0% found this document useful (0 votes)

312 views21 pages

Hypervalent Compounds: G. Sean Mcgrady & Jonathan W. Steed

Uploaded by

Andreea Damian

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PDF, TXT or read online on Scribd

0% found this document useful (0 votes)

312 views21 pages

Hypervalent Compounds: G. Sean Mcgrady & Jonathan W. Steed

Uploaded by

Andreea Damian

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PDF, TXT or read online on Scribd

Hypervalent Compounds ICl3 , and SeCl4 were first reported almost two centuries

ago, appropriate models to describe the bonding in these

molecules have only been developed recently.1 Whilst the
G. Sean McGrady1 & Jonathan W. Steed2 term hypervalent is widely used – and often misused – there
1
University of New Brunswick, Fredericton, NB, Canada is currently no universally accepted definition of the
2
University of Durham, Durham, UK word. Thus, it is instructive briefly to explain the origin
of the term before giving the working definition for
Based in part on the article Hypervalent Compounds by Michael this article.
Lattman which appeared in the Encyclopedia of Inorganic Chemistry,
First Edition.
1.1 The Phenomenon of Hypervalency

1 Introduction and Background 1 In his 1923 monograph, Lewis2 defined the valence of an
2 The Hypervalent Bond: Geometry and Description 2 atom in a molecule as ‘. . . the number of electron pairs which
3 Synthesis and Stability of Hypervalent it shares with other atoms’. Lewis recognized that, through
Compounds 5 a combination of lone or nonbonding pairs and shared or
4 Spectroscopy and Diffraction as Structural Probes 9
bonding pairs, many atoms (other than hydrogen) in molecules
5 Pentacoordinate and Related Structures 10
achieve a total of eight electrons in the outermost shell; he
6 Reactivity of Hypervalent Compounds 12
called this the ‘rule of eight’. Langmuir coined the now more
7 Hypervalent Intermediates and Transition States 14
familiar term ‘octet’.2,3
8 Inter-ligand Hypervalent Interactions 17
Since it was proposed, the octet rule has caused misun-
9 Other Hypervalent Species 18
derstanding and confusion about the status of hypervalent
10 Related Articles 19
molecules, and is often taken to imply that the bonding in
11 References 19
hypervalent molecules is distinct from that in those that obey
the rule. It is an empirical rule based on the formulas of most
compounds known in the early part of last century, and there
Glossary is no reason why there should not be exceptions such as SF6
and PCl5 , as was indeed recognized by Lewis.
Phosphoranes: tbp 10-P-5 phosphorus(V) molecules The term hypervalent was introduced in a classic paper by
Phosphoranides: pseudo-tbp 10-P-4 phosphorus(III) anions Musher1 in 1969 to categorize ‘molecules and ions formed
Pseudo-oct: a structure in which one or two legs of the oct by elements in Groups 15 – 18 of the periodic table in any of
is occupied by lone pairs of electrons their valences other than their lowest stable chemical valence
Pseudo-tbp: a structure in which one, two, or three legs of of 3, 2, 1, and 0 respectively’. This paper led to a surge of
the tbp is occupied by lone pairs of electrons interest in both the theoretical and experimental aspects of
Sulfuranes: pseudo-tbp 10-S-4 sulfur(IV) molecules species that appear to have ‘expanded octets.’According to
Musher, these species involve atoms ‘. . . which exceed the
number of valences allowed them by the traditional theory,
and thus utilize more electron pairs of bonding than provide
Abbreviations
stability in the Lewis – Langmuir theory’. Thus, molecules
ap = Apical; ax = Axial; ba = Basal; 3c/4e = Three-center/ such as SF6 and PCl5 are hypervalent. In addition, according
four-electron; eq = Equatorial; MO = Molecular orbital; to this definition, F3 PO, F2 SO, and even Me3 NO, are also
NBS = N -bromosuccinimide; oct = Octahedron or octahe- hypervalent.
dral; Rf = Perfluorinated hydrocarbon; sp = Square pyramid If hypervalent literally means exceeding the lowest
or square pyramidal; tbp = Trigonal bipyramid or trigonal chemical valence, then even NH4 + is hypervalent, despite
bipyramidal; VB = Valence bond. the fact that the Lewis – Langmuir theory easily accounts for
its stability. Furthermore, if the definition of hypervalency
is restricted to Groups 15 – 18, then this artificially excludes
species such as SiF5 − and SiF6 2− , which are isoelectronic and
isostructural with PF5 and SF6 , respectively. The ambiguities
in the original definition have led to several changes. Today,
1 INTRODUCTION AND BACKGROUND no one would regard NH4 + as hypervalent, while those that
consider PF5 and SF6 hypervalent would classify SiF5 − and
Hypervalent molecules and ions are fascinating species, SiF6 2− in the same way.
since they appear to violate the traditional Lewis – Langmuir At this point, it is clear that whether or not a species is
theory of bonding by expanding the valence shell of hypervalent depends not just on valence, but on the total
a main group element. Although species such as PCl5 , number of valence electrons: a hypervalent molecule or

Encyclopedia of Inorganic Chemistry, Online © 2006 John Wiley & Sons, Ltd.
This article is © 2006 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Inorganic Chemistry in 2006 by John Wiley & Sons, Ltd.
DOI: 10.1002/0470862106.ia094
2 HYPERVALENT COMPOUNDS

ion features an atom surrounded by a total of more than •

•• − •• −
• O•• •
• O ••
eight valence electrons – both bonding and nonbonding. This
−• • • •• −
• •
definition is consistent with the word hypervalent, since the • O
••
S2+ O
••
•
•
• O
••
S O
••
•

expanded octet is a result of increased valence or bond • •

− • •
−
• O • • O •
formation. The major difficulty in this definition is how to •• ••

count electrons. (5)

Can we use the Lewis structure as the determining factor?
If so, there can be no doubt about the hypervalency of PF5 (1) 1.2 Definition of Hypervalency
and SF6 (2). But what about F3 PO (3) and F2 SO (4)?
Initially, hypervalent molecules like PCl5 and SF6 were
described in terms of sp3 dn hybrid orbitals, in an extension
••
•
•• of the spn orbital description used to characterize molecules
•
• F •• •• •• • F •• ••
F •• •
• F F •
•
that obey the octet rule. However, ab initio calculations have
•• •• •• ••
•
• F P •• •• S ••
shown that d orbitals play only a minor role in the bonding
•• •
F ••
••
•
• F
••
F
••
• of hypervalent molecules.5 An alternative approach proposed
• • • •
• F • • F •
•• •• by Pauling invoked combinations of resonance structures
(1) (2) involving four covalent bonds and one or more additional
ionic bonds, as shown in Scheme 1 for PF5 .
Perhaps the most useful definition of hypervalency makes
•
•• •• use of the three-center/four-electron (3c/4e) bond.6 Indeed,
• F •• •
• F ••
Musher in his original paper detailed this type of bonding
•• + •• − ••
•
• F P O
••
•
•
•
• F P O
••
•
• based on the models of Rundle and Pimentel. The 3c/4e bond
•• ••

•
approach has several advantages: (1) it is easily recognizable
• F ••
••
•
• F ••
•• from geometries derived from simple single-bonded Lewis
(3) structures based on Valence-Shell Electron Pair Repulsion
Model rules (VSEPR) (see Valence Shell Electron Pair
Repulsion Model); (2) strategies to stabilize hypervalent
•• ••+ •• − •• ••
bonding are similar for each group; and (3) most inorganic
• • • •
• F
••
S O
••
• • F
••
S O • chemists recognize this type of bond.
••

•
• F •• •
• F ••
The 3c/4e hypervalent bond is used to classify the
•• ••
(4) molecules and ions discussed throughout most of this article.
Section 9.3 briefly mentions some common species referred
to as hypervalent that do not fall into this classification.
While many chemists would draw double bonds to oxygen
because of their knowledge of structure and reactivity,
perfectly acceptable nonhypervalent (octet-obeying) Lewis
structures can also be drawn. In addition, the Lewis structure 2 THE HYPERVALENT BOND: GEOMETRY AND
DESCRIPTION
of SO4 2− (5) can be drawn with only single bonds between
sulfur and oxygen; however, there is little doubt that significant
sulfur – oxygen π -bonding exists. An extreme example of 2.1 Theoretical Description
this conundrum is the conclusion that the ion [F3 CO]− is
hypervalent.4 The carbon – oxygen bond in this ion is very The hypervalent bond is found in molecules and ions in
short, and ab initio molecular orbital (MO) calculations show which an atom is formally surrounded by more than an octet
negative hyperconjugation and high polarity in this bond, of electrons and contains a linear three-center arrangement of
implying significant double bond character and a structure for atoms. One example is PF5 , which has a trigonal bipyramidal
the ion that can be represented as [F3 C=O]− ]. (tbp) geometry. The traditional valence bond (VB) approach

F− F F F F
F F− F F F
F P+ F P+ F P+ F− +P F P+
F F F− F F
F F F F F−

Scheme 1

to describing the bonding in PF5 is to expand the valence z

shell of the central atom to accommodate the extra electrons F
by Hybridization. One of the 3s electrons in the ground-state y F
F P
[Ne]3s2 3p3 electronic configuration of the phosphorus atom is F
promoted to a 3d orbital. Combining the one 3s, three 3p, and x F
one 3d orbitals gives rise to five sp3 d hybrid atomic orbitals,
which are disposed in a tbp arrangement. These hybrid orbitals Energy
overlap with the fluorine 2p orbitals to form five 2c/2e P–F
Ψa
covalent bonds. Indeed, this explanation is the only one given
in most first-year college chemistry textbooks.
An alternative explanation, one that employs a highly ionic
model neglecting d orbital participation, has been proposed.
Described originally by Musher in VB terms, it has an
equivalent MO description, which is given here.7 It is in this P 3pz F 2pz
model that the hypervalent bond is clearly seen. The essential Ψa
features of the MO model in its most rudimentary form
are (1) the central atom uses only valence s and p orbitals;
(2) only one p orbital on the central atom is involved in
bond formation in the linear three-center atomic arrangement;
(3) the remaining central atom valence orbitals bind other
atoms in ‘normal’ bonds or contain lone pairs. The MO Ψb
description of the hypervalent bond is illustrated in Figure 1
for PF5 . (Not shown is the bonding in the xy plane in which
phosphorus uses the 3s, 3px , and 3py orbitals to form three
sp2 hybrid orbitals that bind the three fluorine atoms.) The
three pz atomic orbitals combine to give three MOs. The Figure 1 MO description of the 3c/4e hypervalent bond in PF5 .
in-phase combination of fluorine 2pz orbitals is orthogonal to The bonding in the xy plane is not shown
the phosphorus 3pz orbital and gives rise to the nonbonding
n MO. The out-of-phase combination of fluorine 2pz orbitals
overlaps with the phosphorus 3pz orbital to give the bonding
F F
and antibonding MOs, b and a , respectively. Ten valence F
F
electrons fill the MOs: six go into the three P–F bonding F P F S F
orbitals in the xy plane, and the remaining four fill b and F F
F F
n . b and n , when filled, comprise the 3c/4e hypervalent 10-P-5 12-S-6
bond (see Electronic Structure of Main-group Compounds
and Molecular Orbital Theory). F F
This model can account for the bonding not only in a tbp F F
• F I F
• S
•
•

geometry but also in pseudo-tbp structures in which one or F F

F 12-I-5
more lone pairs occupy vertices of the tbp (Figure 2) (see
also Coordination Numbers & Geometries). For pseudo-oct 10-S-4
geometries, such as square pyramidal (sp) IF5 and square- F
planar XeF4 , there are two sets of hypervalent bonds for each • F
•
•

molecule. Only in the case of an octahedron or octahedral F Cl •• F Xe F

•
•
•

F
(oct) geometry, in which the central atom is surrounded by F
12 valence electrons (such as SF6 ), is the description slightly 10-Cl-3 12-Xe-4
different.7 Here, the sulfur 3s orbital contributes to the bonding 2−
F Cl
and is filled. The three b MOs are filled; this leaves only
• Cl
two n MOs, and these are also occupied. However, for the •
• Xe •• Cl Se Cl
•
oct SeCl6 2− , where 14 valence electrons surround selenium, Cl
F Cl
there are three filled b MOs and three filled n MOs; the
10-Xe-2 14-Se-6
remaining two electrons reside in a stereochemically inactive
4s orbital.
This description is overly simplified, and quantum Figure 2 Examples of various geometries based on VSEPR rules.
chemical calculations have revealed a degree of involvement Also given is the N-X-L notation (Section 2.3). Note that the lone pair
from s and/or d orbitals. Furthermore, π -bonding and of electrons in SeCl6 2− is in a stereochemically inactive 4s orbital

hyperconjugation may also be important to account fully 2.2 What About Period 2 Elements?
for the bonding in these derivatives.4 Indeed, one well-
regarded inorganic chemistry text has called the complete A natural question arises for a bonding model that neglects
d orbitals. If d orbitals are unimportant, why is it that
neglect of s and d orbitals in this bonding model ‘a ruthless
elements of period 2 (the first row) do not form hypervalent
approximation’.8 Nevertheless, this model has served to
derivatives? First of all, there is good evidence that they do in
explain many structural and chemical features of hypervalent
some cases, although under more restrictive circumstances
species. For example, the nonbonding component of the
than elements of periods 3 and below (see Section 9.2).
3c/4e EX2 bond (n ) is localized on the X groups
Importantly, the size of period 2 elements may be too small
or ligands, and has no contribution from the central E to accommodate the extra electron density and increased
atom. This buildup of charge is best accommodated by coordination numbers; there would be too much ligand – ligand
electronegative substituents (see Electronegativity) and, in repulsion, except in unusual environments. Experimental
fact, most of these molecules and ions contain electronegative and theoretical evidence suggests that the tbp geometry
groups at these positions, specifically the axial positions in the nucleophilic displacement mechanism at tetravalent
in a tbp (or pseudo-tbp) and the basal positions of a carbon is a transition state, whereas for silicon it is an
square pyramid (sp). The less electronegative groups will intermediate.9 Quantum chemical calculations10 have added
usually prefer the equatorial sites for the tbp (6) and another dimension to the relative stabilities of hypervalent
apical sites for the sp (7). The bonding model is also in period 2 and 3 elements. These suggest that delocalization
agreement with the usual experimental findings that the of electron density from the axial bonds into the σ * orbitals
3c/4e hypervalent bonds are longer (and weaker) than the of the equatorial bonds results in a significant stabilization
2c/2e bonds. for tbp SiH5 − . For CH5 − , this interaction is destabilizing.
Incidentally, SiH5 − has been observed experimentally11 and
is the only hypervalent species known that possesses just
hydrogen atoms as ligands.
ax ap
eq ba
eq ba ba
eq 2.3 Recent Developments
ax ba
Since about 1990, the availability of fast, high-level
(6) tbp (7) sp
computing power has led to a range of theoretical studies
of formally hypervalent compounds, and of the phenomenon
of hypervalency. Ab initio calculations were carried out by
Both the ionic resonance structures of Pauling (q.v.), and Schleyer, and bond orders were obtained for a large number of
the 3c/4e bonds proposed by Musher, are consistent with hypervalent molecules.4 In all systems studied, the total bond
the octet rule, and also take account of the natural polarity order was found to be less than 4.0; that is, the central
of E–X bonds. They explain the paradox whereby the E atom possessed fewer than eight valence electrons, with
atom in a molecule EXn appears to have more than eight electronegative ligands like O and F producing the lowest
valence electrons by recognizing that these bonds are polar. values. Subsequently, Cioslowski determined bond orders
In formulating the octet rule, Lewis implicitly assumed that using a different method,12 but reached the same conclusions;
each bonding pair of electrons contributes fully to the valence namely that in molecules like SF6 , the S–F bond order is low
shell of both atoms between which it is shared, irrespective (0.64), so that the sulfur atom only contains 7.68 electrons in its
of the polarity of the bond. Ionic resonance structures and valence shell. Gillespie used the electron localization function
3c/4e bonds each locate the excess electron density on the (ELF) to study the same phenomenon.13 The ELF partitions
peripheral X atoms. In practice, most hypervalent molecules electron density in the molecule into regions where there is
possess electronegative X atoms or groups that stabilize this a high probability of finding a pair of electrons of opposite
spin: these regions then correspond to bonding or nonbonding
redistribution of charge. Thus, when bond polarity is taken
electron pairs, and the polarity of bonds is revealed in the
into account, the octet rule may be reformulated so that the
unequal partitioning of bonding pairs between the atoms
valence shell of an atom may contain no more than eight
electrons. Hence the rule may be obeyed by a hypervalent
atom if the ligands are sufficiently electronegative to remove Table 1 Valence-shell electron populations in a variety of formally
hypervalent compounds
from it a substantial amount of electron density in the form of
polar E–X bonds. Molecule Valence shell pop. Molecule Valence shell pop.
It is significant to note that this model places the ‘extra’
electrons on the ligands attached to the central atom and not PF5 5.33 SF6 6.18
PCl5 7.13 SeF6 2.18
on the central atom. Thus the octet may only be expanded in PMe5 9.42 SeMe6 10.98
a formal sense.

involved. Analysis of the ELF in a range of systems in fact 2.6 Primary Literature References
revealed that most hypervalent molecules have a valence shell
containing a total of eight or fewer electrons. However, some Aspects of hypervalent silicon,15 tin,16 phosphorus,17
compounds possessing less electronegative ligands do exceed arsenic,18 sulfur,19 halogens,20 noble gases,21 and pentacoor-
a total of eight electrons in their valence shell, as detailed in dination22 have been reviewed previously. In addition,
Table 1. Gillespie concluded that the bonding in hypervalent comprehensive reviews on organic,23 organometallic,24,25
molecules does not differ in any significant way from that and coordination chemistry26,27 are useful. Several inorganic
in molecules that obey the octet rule, and reiterated that the texts8,28 have a wealth of information, particularly relating
Lewis model is an empirical observation with no grounding to halogenated hypervalent molecules and ions. More recent
in theory. reviews have been published on hypervalent iodine29–31 and
boron/aluminum32 chemistry in organic synthesis, hyper-
valent silicates as organocatalysts,33 bonding descriptions
of hypervalent compounds,13,34,35 inter-ligand hypervalent
2.4 N-X-L Notation
interactions,36,37 cyclic aromatic systems with hypervalent
centers,38 hypervalent xenon chemistry,39 hypervalent tin40
At this point, it is instructive to introduce a system to
and crystal engineering using hypervalent interactions.41 The
classify the bonding around an atom: the N-X-L system.14
topics of hypervalent chalcogen stereochemistry,42 hyperva-
First suggested in 1980, it is particularly useful for the species
lent transition metal catalysed ligand coupling reactions,43
discussed in this article. In this classification scheme, N is
and low coordinate hypervalent phosphorus44 have also
the number of valence-shell electrons formally assigned to the
been covered.
central atom X; and L is the number of ligands directly bonded
to X. The N-X-L designations are illustrated in Figure 2 for
each species listed.
3 SYNTHESIS AND STABILITY OF
HYPERVALENT COMPOUNDS
2.5 VSEPR Theory Basics

It is also useful to review briefly the rules of VSEPR 3.1 Primary Factors Stabilizing the Hypervalent Bond
theory with respect to the two simple molecules PF5 and SF4
(Figure 3). Only when the central atom possesses no lone pair There are two main principles for the stabilization of
electrons and is surrounded by simple, identical ligands is the hypervalent bond. The first has already been stated:
an ideal geometry realized. Thus, PF5 will have an exact tbp electronegative groups stabilize the hypervalent bond. This is
geometry. However, the pseudo-tbp geometry of SF4 shows illustrated by reference to equations (1 – 6), where a halogen or
distortions caused by repulsion from the sulfur lone pair. The halide source reacts with a nonhypervalent species to produce
spatially more demanding lone pair occupies an equatorial site, a hypervalent product; for tbp or pseudo-tbp geometries, the
which provides it with more space than an axial site would halogen occupies the axial positions.15,17,19,20,28 Addition may
allow. Note that both the Fax –S–Fax and Feq –S–Feq bond or may not be accompanied by oxidation of the central atom.
angles are contracted from the ‘ideal’ angles of 180◦ and 120◦ , Moreover, addition is not limited to halogens; for example,
respectively. However, the equatorial angle is contracted to a nitrogen and oxygen bases are perfectly suitable (equations 7
greater extent. This contraction will have significance when and 8).27
10-X-5 and 10-X-4 geometries are compared in Section 5.4
for more complex ligands. Cl
Cl2
PhI Ph I
(1)
Cl
F F 10-I-3
F • F F
F P • S F
F F2
F Xe Xe
F (2)
F
Angle Fax –X–Fax (deg) 180 173.1
10-Xe-2
Angle Feq –X–Feq (deg) 120 101.6
Distance Fax –X (pm) 158 164.6 F
Distance Feq –X (pm) 153 154.5 MoF6 R
R3P R P
R (3)
F
Figure 3 Structures of PF5 and SF4 10-P-5

− −
F
Ph O
F−
Ph2SiF2 F Si (4) HOCH2CH2OH R Si O
O (10)
Ph (RO) 3SiR
F base O
10-Si-5 10-Si-5
F
2F2
Xe F Xe F
(5)
−
F +
+ P P−
12-Xe-4 (11)
−
F
F2 CF3
(CF3)2S S 3
CF3 (6)
F 12-P-6
10-S-4 OH O Cl O
−4 HCl
Cl NCMe PCl5 + 2 P
SnCl4 + 2MeCN Cl Sn Cl OH O O
(7)
MeCN Cl 10-P-5

12-Sn-6 (12)

Me OSiMe3 O
OSMe2 −2 Me3SiF
Me2SnCl2 + 2Me2SO Cl Sn OSMe2
(CF3)2SF2 + SF2
(8) O
Cl Me OSiMe3
10-S-4
12-Sn-6
(13)

Substituent site preferences in a tbp are based on (what

is commonly referred to as) an apicophilicity scale which
takes into account several factors, so the ordering of
axial/equatorial site preferences may not always strictly I I
follow electronegativity expectations (Section 5.1). For a S S
sp geometry, the more electronegative groups occupy the
basal positions.
The second principle may be even more important than
the first: the hypervalent bond is stabilized by the steric (8) (9)
constraints of small rings. Specifically, this usually means the
incorporation of the central atom into four- and five-membered
rings. These rings stabilize 90◦ bond angles about the central The importance of rings in supporting these hypervalent
atom, and such an orientation introduces the least strain in systems is clearly shown by the relative stabilities of
the ring. This principle is often stated as the preference cyclic versus acyclic structures. For example, (8) undergoes
of four- and five-membered rings to span axial/equatorial slow decomposition at ambient temperature, while (9)
positions in a tbp. Equations (9 – 11) illustrate the principle for shows no decomposition over several months.20 A more
reactions involving the synthesis of hypervalent products from dramatic demonstration of the stability introduced by rings
nonhypervalent reactants.15,17 Rings can also be incorporated is illustrated for sulfuranes (10) and (11) in equations (14)
via substitution reactions using hypervalent starting materials and (15).6 However, recently the first noncyclic 10-S-5
(equations 12 and 13).17,19 sulfuranide dioxide anion, [(CF3 )3 SO2 ]− has been reported
and structurally characterized. The compound exhibits a tbp
structure with equatorial oxygen atoms.45
OR
O P OR
O OR OC(CF3)2Ph
(RO) 3P + O (9) S Ph
H2O
HOC(CH3)2Ph + Ph2SO
Ph (14)
O OC(CF3)2Ph
10-P-5 (10)

F3C CF3 t-Bu

F3C CF3
O
O O
H+, H2O
S no reaction Br N X
boil (15)
O O
O
F3C F3C CF3 t-Bu
CF3
(11) (15) (16a) X = P
(16b) X = As
Judicious choice of ring systems can even overcome the (16c) X = Sb
usual preference of electronegative ligands for axial sites. For
example, it is well known that the usually tetrahedral 8-Si-4
silanes can function as Lewis acids, particularly when very
electronegative substituents are attached to silicon. Molecule H
(12) illustrates the formation of a five-membered ring through
N N
intramolecular coordination.15 Here, the steric requirements
of the ring to span axial/equatorial positions outweigh the N P H N P
N N (16)
electronegativity preferences, and one of the two fluorine N N
substituents is forced into an equatorial site. 10-P-5 8-P-3
(17a) (17b)

F
F Compound (17) is synthesized by the treatment of the
Si
Me appropriate cyclic amine with tris(dimethylamino)phosphine
NMe2 at 100 ◦ C, resulting in the elimination of three moles of
dimethylamine. The products obtained are dependent on the
number of methylene groups bridging the nitrogen atoms.
(12) When all four bridges are ethylene, (CH2 )2 , only (17a) is
observed; when all are trimethylene, (CH2 )3 , only (17b) is
Polydentate ligands also lead to isolation of derivatives with found. When there are two of each type, both tautomers
hypervalent bonds. Examples of tetradentate-ligated species are present.
are the ‘atranes’ (13)22,46,47 and porphyrins (14).48 Various
linkages, both saturated and unsaturated, can connect the
3.2 Other Stabilizing Factors
oxygen and nitrogen ligand atoms in the atranes, and the R
substituent on the porphyrin ring can be varied systematically.
The above principles are the most important factors in
Planar tridentate-ligated examples are (15)6 and (16).49 In fact,
the stabilization of the hypervalent bond. However, there are
10-X-3 (X = P, As, Sb) species can only be isolated under the
other general considerations to take into account.6 One is
severe constraints of the ligand illustrated. A striking example
the preference for a relatively electropositive central atom:
of the delicate balance that exists between ligand and product
a positive charge develops at this center, and is most easily
is shown for (17) in equation (16).50
accommodated by such an atom. In addition, an electropositive
equatorial ligand will assist in stabilizing this positive charge at
R the hypervalent center. Other factors, primarily governing site
R
preference and orientation in tbp and pseudo-tbp geometries,
R R have significance, and these are elaborated in Section 5.
N Cl N
X
3.3 Periodic Trends
N N Cl N
O R There are few periodic generalizations that can be
O X R
O made concerning hypervalent molecules, since the factors
L R R contributing to stability, such as oxidation potential, central
(13) X = Al, Si, P (14) X = Sn, Ge atom size, type of ligands, and ionic versus covalent bonding
type, all interact in a complex manner. However, some general
trends are evident.

3.3.1 Inert Pair and Alternation Effects 3.3.3 Oxidizability of the Central Atom

Electronegativity generally decreases down a group in For hypervalent molecules formed by oxidation, the ability
the p-block, and it may be thought that higher oxidation to remove electrons from the central atom is a key factor.
states are therefore more stable for the heavier congeners The formation of noble gas derivatives,47 such as XeF2 , is
in a group. However, this is not the case, as insertion of related to the ionization energy of the element in a rather
the first row of transition elements and of the lanthanide straightforward manner. In fact, Bartlett originally reasoned
elements in the third and fifth periods causes the p-block that since PtF6 oxidized molecular oxygen to give O2 + PtF6 − ,
elements directly following these changes to have a higher xenon should be similarly oxidized, since the ionization
electronegativity than would otherwise be the case. Group 15 energies of O2 and xenon are comparable. The ionization
exemplifies this phenomenon admirably: the electronegativity energies of the noble gases above krypton are prohibitively
of As (2.2) is identical to that of phosphorus, and that high to allow this kind of chemistry. Indeed, although argon
of Bi (2.0) is almost the same as that of Sb (2.1). This has now been activated photochemically at 10 K to form
Alternation Effect in electronegativity down the Group affects HArF,51 only xenon and krypton form tractable compounds.
the stability of higher oxidation states for As and Bi: a (see Noble Gases: Inorganic Chemistry). The formation of
reduction in ionic resonance energy accompanies the increase hypervalent organoiodine(III) dihalides (19) is directly related
in electronegativity and is reflected in weaker bonds to F, to the oxidizing ability of the ligating halogen (equation 17).20
O and Cl than would otherwise be the case. Thus, PCl5 and This equilibrium is shifted to the left for L = Cl and to the
SbCl5 are stable molecules at ambient temperatures, whereas right for L = Br and I.
AsCl5 decomposes above −50 ◦ C, and BiCl5 has never been
reported. Operating in tandem with this phenomenon is the L
Inert Pair Effect, whereby a monotonic decrease in bond Ph I Ph–I + L2
strengths down a group serves to destabilize higher oxidation (17)
L
states for the heavier congeners. The two effects conspire in 10-I-3 8-I-1
the fifth period, and hypervalent compounds of bismuth form (19)
only under the most forcing conditions.

3.3.4 Central Atom Charge

3.3.2 Increase of Coordination Number with Size
Central atom charge is also important, particularly for
The ability to increase coordination number with central hypervalent species formed by simple addition. This is best
atom size within a group is perhaps the most generally reliable illustrated by trends in the Group 14 derivatives R4−n MLn
periodic trend. The increased coordination shows up distinctly (M = Si, Ge, Sn, Pb; L = I, Br, Cl, F). In general, the
in period 5. For example, no complex forms between pyridine Lewis acidity of the central atom increases in the order
and Me3 SiCl, while Me3 SnCl· pyridine is stable.27 In addition, L = I < Br < Cl < F, and n = 1 < 2 < 3 < 4. For n = 1,
trialkyltin halides have a much greater tendency to associate complexes appear to be limited to tbp 1:1 adducts, while for
in the solid state than do their silicon and germanium analogs; n > 1, oct 1:2 adducts are common.27
for example, trimethyltin fluoride (18) is associated in the
solid state. Even in solution, tributyltin fluoride associates to
3.3.5 Covalent Versus Ionic Bonding
give polymeric structures. Likewise, PF5 and AsF5 are both
monomeric, but SbF5 is associated, even in the gas phase. The tendency to form covalent rather than ionic bonds
SF4 and SeF4 are monomeric; TeF4 in the solid state forms is crucial in the formation of hypervalent compounds.
polymeric 12-Te-5 pseudo-octahedra via fluoride bridges. Incorporation of fluoride as a ligand usually stabilizes covalent
Size is also a factor for the linear trihalide monoanions X3 − : species. For example, PF5 is covalent. However, PCl5 is
in general, their thermal stabilities increase with increasing characterized by the equilibria shown in equations (18) and
central atom size.47 (19). In the gas and liquid phases, the molecular form exists,
while in the solid state it is ionic, consisting of PCl4 + and PCl6 −
ions. In solution in nonpolar solvents, the molecular form
Me Me is favored, while the ionic form described in equation (18)
F Me predominates in polar solvents. At low concentrations, some
Sn Sn PCl4 + and Cl− may be present owing to the equilibrium in
F Me F equation (19). For equation (20) (R = alkyl and aryl), if L is
Me Me
a reasonably basic anion such as Cl, Br, I, or OPh, the ionic
(18) phosphonium salt (20) is favored. With L = F or O-alkyl, the

pentacoordinate species (21) is observed.52,53 of fluorine resonances at low temperature; these coalesce
to a single feature at higher temperatures. For PF5 and
2PCl5 −
−−
−−−− PCl4 + + PCl6 − (18) RSiF4 − , only one resonance is observed, even at low
temperatures. However, for the derivatives RPF4 and R2 SiF3 − ,
PCl5 −
−−
−−−− PCl4 + + Cl− (19)
behavior similar to SF4 is observed. Exchange mechanisms
+ −
R4 P L −
−−
−−
−− R4 PL (20) have been advanced to explain this fluxional behavior (see
8-P-4 10-P-5 Section 5.2). Secondly, the chemical shift can usually be
(20) (21)
correlated with coordination number: higher coordination
leads to resonances at higher fields. For example, 31P the
chemical shift values for PCl3 , PCl4 + , PCl5 , and PCl6 − are
219, 96, −80, and −281 ppm, respectively. However, this
4 SPECTROSCOPY AND DIFFRACTION AS trend is highly substituent-dependent, and similar ligands must
STRUCTURAL PROBES be present to rely on such a correlation. A third application
is the use of coupling constants to assign substituent sites
in a tbp or pseudo-tbp. Coupling constants are dependent
4.1 Diffraction Techniques
on the amount of s character in a bond: the greater the
Leaving aside single-crystal X-ray diffraction, which has s character, the larger the coupling constant. A dramatic
produced the vast majority of structural data for compounds illustration of this phenomenon is found in the low-temperature
13
of all types, gas-phase electron diffraction deserves special C NMR spectrum of Me(CF3 )3 PF (22), a tbp molecule
mention in the study of hypervalent molecules. Many that has one fluorine and one CF3 group occupying axial
hypervalent p-block species are gases or volatile liquids positions. The one-bond P–C coupling to the equatorial CF3
at ambient temperatures, and hence are not amenable to groups is 258 Hz whereas that to the axial CF3 is only
study by conventional X-ray diffraction techniques. Main 17 Hz.58
group molecules like PF5 , SF4 , and ClF3 , and noble gas
compounds like XeF6 were structurally determined by electron F
diffraction during the 1960s, and these studies were expanded CF3
to encompass important mixed-ligand species like the methyl Me P
CF3
and chloro-substituted derivatives of PF5 . These gas-phase CF3
studies produced the main body of evidence around which
(22)
VSEPR theory developed.54

4.2 Vibrational Spectroscopy

IR and Raman spectroscopy are extremely useful for the 4.4 Other Spectroscopic Techniques
determination of structures of hypervalent species, particularly Although less important than gas-phase electron diffrac-
for simple molecules where complete spectral assignments tion, microwave spectroscopy is a valuable technique for
can be made.55 For mixed halide systems in tbp or pseudo-tbp the structural characterization of gases and volatile liquids.
geometries, such as PF2 Cl3 or SF2 Cl2 , vibrational data can For example, HPF4 and H2 PF3 (Figure 4) were shown in a
discriminate unambiguously between possible isomers. The combined electron diffraction and microwave spectroscopy
fast timescale of vibrational spectroscopy proved particularly study to be tbp species in which the hydride ligands occupy
useful in showing that the 14-X-6 species BrF6 − is octahedral equatorial sites.59
in solution; in contrast to IF6 − , where the nonbonding Mössbauer Spectroscopy has also proved useful for the
electron pair displays stereochemical activity.56 For high- study of hypervalent species, since many of the central atoms,
symmetry molecules, rotational-vibrational spectroscopy can such as Sn, Sb, Te, I, and Xe, are suitable for study by
afford accurate molecular constants that permit a full structural this technique.60 Gas-phase UV photoelectron spectroscopy,
determination of molecular structure, as was demonstrated while not particularly important for geometry elucidation, has
elegantly for H3 PF2 (Figure 4).57

F F F
4.3 NMR Spectroscopy F H H
H P F P H P
Multinuclear NMR spectroscopy is indispensable to the F H H
F F F
study of hypervalent species for several reasons. First of
all, exchange processes can be identified and measured. For
example, the 19 F NMR spectrum of SF4 shows two types Figure 4 Equatorial H atoms in tbp hydrido derivatives of PF5

been used to obtain information on the electronic structures of F CF3 CF3 F

hypervalent molecules.61 X-ray photoelectron spectroscopy is CF3 F F CF3
F P F P F P F3C P
also useful for determining charge distributions, particularly F F F CF3
in demonstrating the greater negative charge on the axial F F CF3 F
substituents in a tbp.62 60% 40% 100% 100%

Figure 5 Trifluoromethyl derivatives of PF5

5 PENTACOORDINATE AND RELATED

STRUCTURES One particularly intriguing family of molecules is the
trifluoromethyl derivatives of PF5 , illustrated in Figure 5. The
structure adopted by these molecules depends strongly on
The greatest body of work in hypervalent chemistry
their makeup: three CF3 groups occupy the equatorial sites
has been carried out on 10-X-5 structures, most often tbp
in a tbp, two occupy the axial ones, and a single CF3 moiety
phosphoranes. However, the results have been generalized in
occupies either position with statistical probability.67 The CF3
most cases to include all pentacoordinate main group elements.
ligand has a group electronegativity comparable to that of
They also have implications for pseudo-tbp structures such as
Cl, and so electronic factors would place it preferentially in
the 10-S-4 sulfuranes. Some of the more important aspects are an axial site. However, the steric bulk of the ligand appears
described in this Section. to override these considerations, so that these phosphoranes
adopt structures that minimize contacts between CF3 groups.
5.1 Apicophilicity This series of molecules demonstrates that apicophilicity is a
complicated phenomenon, and that each case should be judged
Apicophilicity can be defined as the change in energy on its merits.
when an apical (or axial) ligand and an equatorial lig-
and in a tbp structure are exchanged; the more apicophilic
5.2 Site Exchange: Pseudorotation
ligand prefers the axial site. This relative scale has been
constructed and quantified by experimental and theoretical One of the unique aspects of hypervalent chemistry is the
techniques. For example, Trippet63 devised a scale based on fact that two different types of bonds can exist in one molecule
dynamic NMR measurements of pentacoordinate phospho- (for example, the axial and equatorial P–F bonds in PF5 ) and
ranes. Apicophilicity is dependent on several factors such that these bonds may interconvert by an isomerization process.
as electronegativity, π -bonding ability, and size of the lig- On account of its slow timescale, NMR spectroscopy is the
and. This scale has been examined by many researchers, ideal method to study such exchange processes, and PF5
and no two approaches give exactly the same ordering. was one of the first pentacoordinate molecules to be studied
However, the following is a general ordering of decreasing using this technique. Only one resonance (a doublet due to
apicophilicity: F > H > CF3 > OPh > Cl > SMe > OMe > 31
P coupling) is observed in the 19 F NMR spectrum down
NMe2 > Me > Ph. Caution is necessary in using this scale: to −190 ◦ C. However, RPF4 derivatives display temperature-
some results imply that Cl may be more apicophilic than F in dependent spectra: at ambient temperatures only one fluorine
certain systems.64 resonance is seen, while at low temperatures resonances owing
Theoretical work on the model phosphorane PH5 has to inequivalent fluorine atoms are observed. Berry68 first
shown that π -acceptor ligands prefer axial sites and π - proposed an intramolecular exchange process to account for
donors favor equatorial positions in a tbp.65 However, a these observations. He showed that, in a tbp (Figure 6(a)),
significant difference is observed when the orientation of a bending two of the equatorial atoms away from each other
π -donor p orbital at an equatorial site is examined for a 10-P-5 and the two axial atoms toward each other equilibrates these
phosphorane and a 10-S-4 sulfurane.66 For the phosphorane, atoms at the basal sites of a sp transition state (b). Continuing
the preferred orientation is in the equatorial plane (23), while this deformation results in an interchange of the atoms at
for the sulfurane it is perpendicular to it (24). The difference the axial and equatorial positions (c). This process is known
arises from the interaction of the ligand donor orbital with the
sulfurane lone pair.
1 1
4 4
4 1
3 3 3
2 2
5 5 2 5
•
P • S (a) (b) (c)

(23) (24) Figure 6 The Berry pseudorotation process

as the Berry pseudorotation (or simply pseudorotation, see The most detailed structural work on pentacoordinate
Pseudorotation). Note that one of the equatorial atoms, 3, structures has been carried out and compiled by Holmes,17,22
remains fixed in this scheme and acts as the fulcrum for the and some of his findings are summarized here. Basic VSEPR
process. Continuation of this process with different equatorial rules can account qualitatively for geometries with simple
pivot atoms results in an equilibration of all five atoms. The acyclic ligands; for example, the series Men PF5−n (n = 1 – 3).
energy barrier to this process is very low and for PF5 cannot However, as ligands become more complex, other factors
be measured by NMR spectroscopy; however, introduction of predominate. Preference rules have been derived for both
other substituents (as in RPF4 ) raises the exchange barrier to the tbp and sp geometries and are listed here in order of
a point where it can be frozen out on the NMR timescale. probable importance.
For some species of the type R2 PF3 , exchange does not occur For the tbp:
even at ambient temperature, owing to the necessity of placing
one or more R group in an energetically unfavorable axial 1. Four- or five-membered cyclic systems preferentially span
position. axial/equatorial positions.
Pseudorotation has also been shown to be important in 2. The most electronegative ligands preferentially occupy
10-S-4 and 10-Si-5 species such as SF4 19 and R2 SiF3 − .15 axial sites.
While pseudorotation is usually invoked to explain the 3. π -Donor ligands, in general, are positioned at equato-
observed exchange phenomena, alternative intramolecular rial sites.
processes have been proposed, such as the Turnstile 4. Steric effects are minimized by locating bulky groups in
Mechanism.52 This involves rotation of a pair of ligands equatorial positions.
on one side of the tbp and the remaining three on the other
For the sp:
side. Both Berry and turnstile mechanisms result in a similar
exchange, albeit via different transition states. It is difficult to 1. Four- or five-membered cyclic systems preferentially span
differentiate these mechanisms experimentally; however, the cis basal positions.
structural data described in the next Section appear to support 2. The most electronegative ligands preferentially occupy
the Berry process. basal sites.
3. π -Donor ligands, in general, are positioned at the
apical site.
5.3 Structural Distortions in the Solid State
4. Steric effects are minimized by locating a bulky group in
The low barrier to exchange of axial and equatorial the apical position.
substituents suggests that structural distortions of 10-X-5
In addition, factors favoring the sp over the tbp have been
derivatives from a tbp might be observed in ground-state
identified. The most important appears to be the incorporation
geometries as well. Calculations show that the lowest energy
of unsaturated five-membered rings into 10-X-5 species.
arrangement of five points on a sphere is a tbp; however, the
Apparently, less ring strain is introduced when such rings
sp is only slightly less stable, and certain substituents might
span cis basal positions in a sp rather than axial/equatorial
prefer this geometry. The idealized angles for the sp are 105◦
sites in a tbp. In fact, the sp geometry predominates when two
(ap/ba), 150◦ (trans-ba/ba), and 86◦ (cis-ba/ba), as depicted in
such rings are present, as in structure (26).
structure (25).17

ap OLO
105° P
O O
ba
ba ba (26)
86° ba
150°
Referring to geometries like (26) as a sp or RPF4 as a
(25)
tbp are only approximations, since only a species with all
five substituents identical (like PF5 ) will exhibit an exact tbp
It is important to note that the sp of (25) is related to the geometry. In fact, the geometry of (26) is close to a sp and
IF5 sp (see Figure 2) in the sense that the ligands attached that of RPF4 is close to a tbp. But how close? A simple
to the central atom are disposed at the vertices of a similar metric plots the axial and equatorial angles, versus a measure
polyhedron. However, they differ electronically, since the sp of the distortion coordinate, the dihedral angle between faces
of (25) is a 10-X-5 species and that of IF5 is 12-X-5. The 124 and 245 (see Figure 6(a)). A more complicated scheme
central atom in the sp of a 10-X-5 species will lie above the involves determining all of the dihedral angles.17,22 No matter
basal plane, while that in a 12-X-5 species will lie below the which method is used, the findings are essentially the same.
basal plane owing to lone pair/bond pair repulsion. Virtually all of the known structures of 10-P-5 molecules are

either close to a tbp or sp geometry, or show distortions that to CF2 and CF3 groups, respectively (equations 23 and 24).73
lie along the Berry pseudorotation coordinate (the conversion ClF3 is a powerful fluorinating agent for inorganic chlorides
of (a) to (b) in Figure 6). This has now been extended to and oxides (equations 25 and 26).
most other 10-X-5 species, both neutral and ionic. The fact
that these ground-state geometries closely approximate the PCl5 + 4H2 O H3 PO4 + 5HCl (21)
Berry coordinate lends support to the pseudorotation exchange SF4 + 2H2 O SO2 + 4HF (22)
mechanism described in Section 5.2.
Me2 CO + SF4 Me2 CF2 + F2 SO (23)
PhCO2 H + 2SF4 PhCF3 + 2F2 SO + HF (24)
5.4 Apicophilicity ‘Anomalies’ in 10-S-4 Sulfuranes
AgCl + ClF3 AgF2 + 1
2
Cl2 + ClF (25)
In general, the trends found in 10-X-5 derivatives find NiO + 2
ClF3 NiF2 + 1
Cl2 + 1
O (26)
3 3 2 2
parallels in 10-X-4 species; however, the presence of a
nonbonding pair of electrons on the central atom can alter
certain aspects, such as the equatorial lone pair orientation Octahedral hypervalent halides, on the other hand, are much
described in Section 5.1. More importantly, the Fax –S–Fax less reactive (see Coordinative Saturation & Unsaturation).
angle in SF4 (Figure 3) suggests that the ring strain introduced For example, PF6 − is a widely used noncoordinating anion
by having a small ring span two equatorial positions should be (see Noncoordinating Anion or Cation); SiF4 · bipyridine is
less important than in 10-X-5 species. In fact, sulfurane (27) stable in the presence of moisture; and SF6 is remarkably inert:
has the ring spanning equatorial sites.69 it can be treated with steam at 500 ◦ C or with molten KOH
without any effect. It is nontoxic and used as an insulating gas
in high voltage applications.
OC(CF3)2Ph Many coordinatively unsaturated species are good Lewis
Me
CF3
acids, owing to the positive charge induced on the central
S atom as a result of electronegative substituents. For example,
O CF3
PF5 , and to an even greater extent AsF5 and SbF5 , are
OC(CF3)2Ph excellent fluoride ion acceptors, yielding robust XF6 − anions
(27) that stabilize such acidic cations as S4 2+ and XeF5 + .
Oxidative Addition is also common for those central atoms
that can increase their oxidation state (see Oxidation Number)
5.5 The Puzzling SbPh5 Structure8,47 (equations 27 and 28). Substitution of halogen by organic
groups is useful for the preparation of organo derivatives, as
The vast majority of pentacoordinated molecules unper- mentioned in Section 3.1 (equations 12 and 13).
turbed by rings adopt regular or approximate tbp structures:
for example, the organic derivatives Ph5 P, Ph5 As, Me5 As, and SF4 + ClF SF5 Cl (27)
Me5 Sb. However, Ph5 Sb is sp in the solid state and appears
10-S-4 12-S-6
to retain this geometry in solution. No adequate explanation
for this behavior has been advanced. Even (p-MeC6 H4 )5 Sb ClF3 + F2 ClF5 (28)
is tbp. The only other simple species shown unambiguously 10-Cl-3 12-Cl-5
to favor a sp over a tbp structure is InCl5 2− as the NEt4 +
salt,70 although this appears to be highly dependent on crystal
packing since the analogous PPh4 + and PPh2 Cl2 + salts each 6.2 Silicon in Organic Synthesis15
contain tbp InCl5 2− .71,72
Hypervalent silicon compounds have found wide utility
in organic synthesis. In general, pentacoordinated anionic
silicates are more reactive toward nucleophiles than
are tetracoordinated silanes. For example, Mes2 SiF2 is
6 REACTIVITY OF HYPERVALENT COMPOUNDS
unreactive toward water, while (the 18-crown-6 potassium
salt of ) Mes2 SiF3 − is completely hydrolyzed within minutes.
6.1 General Similarly, the pentacoordinate anion HSi(OEt)4 − is an
effective reducing agent for aldehydes, ketones, and esters
Sterically unsaturated hypervalent halides are quite at or below room temperature (Scheme 2); no such reaction
reactive. Typical reactions involve the transfer of halogen and occurs with HSi(OEt)3 . The difference in relative reactivities
a reduction in coordination number. For example, hydrolysis of hypervalent and nonhypervalent species is relevant to the
is usually facile and sometimes violent (equations 21 and 22). intermediates proposed in Section 7.6.
Many of the fluorides are excellent fluorinating reagents. SF4 The oct 12-Si-6 dianion RSiF5 2− has been carefully studied,
is useful for the conversion of ketones and carboxylic acids and reactions with this reagent are stereospecific. Some of

RCH2OH has been recently reviewed.29–31,76

RCHO
I(OAc) 3

HSi(OEt)4− R1R2CHOH + O

R1COOR2 R1COR2 O
(28) 12-I-5
R1CH2OH R1R2CHOH (29)
I(OAc)

Scheme 2 R 1R2CO + 2AcOH + O

O
these are illustrated in Scheme 3. For R = alkyl, treatment 10-I-3
with N -bromosuccinimide (NBS), bromine, or copper(II)
O MeO OMe
bromide yields alkyl halides with inversion of configuration
at carbon. For R = alkenyl, cleavage by halogens leads PhI(OAc) 2
OH
(30)
to alkenes with retention of configuration. By comparison,
MeOH/KOH
8-Si-4 alkenyltrimethylsilanes proceed with inversion of
configuration under similar conditions. This is a result of
the usual trans addition and anti elimination in the latter case,
6.4 Basicity of Hypervalent Lone Pairs
while direct electrophilic displacement may account for the
stereochemistry in the former. Reaction of RSiF5 2− with other 10-X-4 derivatives possess lone pairs of electrons in an
metal salts (Ag+ , Cu+ , P2+ ) can lead to reductive coupling. equatorial position that may show donor ability toward metals
and other Lewis acids. For example, SF4 can be oxidized
6.3 Hypervalent Iodine Reagents to OSF4 ; however, the BF3 complex of SF4 exists as the
ionic salt [SF3 ][BF4 ]. The high degree of s character in the
Hypervalent organoiodine compounds have found wide equatorial lone pair orbitals of 10-S-4 sulfuranes and 10-
utility in organic synthesis. Primary and secondary alcohols P-4 phosphoranide anions should lower their donor ability
can be oxidized to aldehydes and ketones with the 12-I- relative to the excellent ligands R2 S and R3 P. In addition,
5 compound (28), according to equation (29).74 α-Hydroxy the presence of very electronegative groups might reduce
dimethyl acetals can be synthesized under basic conditions their basicities; however, since PF3 is an excellent ligand,
with the 10-I-3 reagent PhI(OAc)2 (equation 30).75 The topic the presence of electronegative groups should not ipso facto
diminish coordinating ability. Compounds that can be formally
considered complexes of phosphoranides exist, (29) and (30),
RBr (R = alkyl) but they are usually prepared by routes other than simple
R2 inversion coordination, such as nucleophilic attack on pentacoordinated
NBS or phosphorus77 and oxidative addition of fluorine to a metallated
Br2 or
Ag+ or CuBr2
difluorophosphine78 (equations 31 and 32). Note the use of the
Cu+ or hypervalent fluorinating reagent in the latter reaction. Perhaps
Pd2+ halides these are best viewed as metallasubstituted phosphoranes.
However, the 10-X-3 species (16) show excellent donor
RSiF52−
properties,79,80 and both lone pairs can be coordinated under
suitable conditions (Scheme 4).
3-ClC6H4CO3H Br2
O Cl O
P + Na[Mn(CO)5]
R′ H O O − NaCl
ROH
retention C C
H Br Mn(CO)5
O O
(R = trans-R′CHCH–) P
retention O O
(29)
Scheme 3 (31)

t-Bu t-Bu t-Bu

O O O
Ag+ MnCp(CO)2
Ag+ 2MnCp(CO)2•THF
N P N X X = As, sb
N X
X=P
MnCp(CO)2
O O O
t-Bu 4 t-Bu t-Bu
10-P-4 10-X-3 10-X-5
(16a) X = P
(16b) X = As
(16c) X = Sb

Scheme 4

PEt3 PEt3 at the central atom of a tetracoordinated molecule or ion.

CO CO
Indeed, many 10-P-5 and 10-Si-5 species can be considered
Cl Ir PF2 + XeF2 Cl Ir PF4 + Xe
(32) as stabilized intermediates formed through such a process.
Cl Cl Usually, it is assumed that the attacking group enters at an
PEt3 PEt3
(30) axial position, and the leaving group leaves from an axial
position. Pseudorotation may occur in the tbp intermediate to
place the leaving group at an axial position. For phosphorus,
this is a well documented process. For silicon, the entry
7 HYPERVALENT INTERMEDIATES AND position appears to be usually axial, but some data suggest
TRANSITION STATES equatorial entry for organometallic reagents. Since the axial
bonds are longer and weaker, it is reasonable that a group will
7.1 General Considerations for Intermediates leave from this position.
The possible pathways for reactions at tetracoordinated
Some of the most important hypervalent species are phosphorus and silicon are summarized in Figure 7. Path
the reactive intermediates formed by nucleophilic attack 1 is directly analogous to carbon chemistry, in which

−
A
B D
D −A− C
B Path 1: leaving group A
C
Nu Nu
inversion
+ Nu−

− −
A A A A
+ Nu− D C −B−
D B B D
C pseudo- Nu
B C rotation Nu C
Nu D
Retention
+ Nu− Path 2: leaving group B

−
A Nu
D −A−
Nu D Path 3: leaving group A
C
B C
B Retention

Figure 7 Pathways for nucleophilic substitution at tetracoordinated phosphorus and silicon. Path 3 is postulated for silicon only81

inversion of configuration is observed; however, for carbon (35) are produced in an approximate 60:40 ratio. The exact
the pentacoordinate structure is a transition state, not mechanism is somewhat more complicated, but the key points
an intermediate. Path 2 involves pseudorotation of the are that the intermediates are stabilized by the ring orientation
intermediate and leads to retention of configuration. Only (leading to enhanced rates), and that formation of (35) can
for silicon has equatorial entry been suggested via Path only occur via pseudorotation.
3. Some very important reactions proceed through 10-P-5
intermediates, such as the Wittig reaction.52,53 Several specific
examples from phosphorus, silicon, and sulfur chemistry are 7.3 Acyclic Phosphonium Salts
discussed below to illustrate the principles stated above and to In general, hydrolysis of acyclic phosphonium salts leads to
demonstrate the importance of reactions involving hypervalent inversion products via Path 1. The incoming group will attack
intermediates. at the tetrahedral face, resulting in a tbp with the leaving group
at the opposite axial position. This mechanism can be modified
7.2 Hydrolysis of Cyclic Phosphate Esters by increasing the steric bulk of substituents. For example, base
hydrolysis of (36) leads to retention of configuration. The t-
Cyclic phosphate esters containing five-membered rings butyl group effectively prevents the incoming nucleophile
hydrolyze 105 – 108 times faster than their acyclic analogs. from attacking at a face that would put the preferred group
However, for six- and seven-membered rings, hydrolysis rates (CH2 Ph, owing to electronegativity and leaving ability) in an
are comparable to those of their acyclic congeners. From axial position. Thus, the initial intermediate formed is (37),
the principles already discussed, these data suggest that the in which the bulky t-butyl group is in an unfavored axial
preference for five-membered rings to span axial/equatorial position. Instead, pseudorotation places the leaving group
positions in a tbp may be a factor in the rate enhancement. (PhCH2 ) in the preferred axial position for elimination of
In fact, Westheimer82 developed a now well-established toluene via Path 2, which gives the final inverted product,
mechanism based on this fact; one that not only accounts (t-Bu)(Ph)MeP=O.
for the observed rate enhancement but also for product
distributions where pseudorotation of an intermediate occurs. t-Bu
For example, the acid-catalyzed hydrolysis of (31) gives two t-Bu
+ Me
phosphorus products; one ring opened and the other with P Me PhCH2 P
Ph
the ring intact. X-ray diffraction analysis of (31) and other PhCH2 Ph
OH
related cyclic systems shows the O–P–O angle in the ring
(36) (37)
to be 99◦ ; hence spanning the axial/equatorial positions in a
tbp relieves about 9◦ of ring strain. The proposed mechanism
(Scheme 5) involves initial nucleophilic attack by water to 7.4 Enzyme Systems17,22
give (32). If displacement from this intermediate occurs, (34)
is formed. However, pseudorotation of (32) can occur to give The wealth of structural and mechanistic information
(33), and this would lead to the final product (35). For the available for pentacoordinated phosphorus has provided a
specific case of hydrolysis of (31), the products (34) and firm foundation upon which to explore more complicated

O O O
O
P H2O O O
OMe MeO P HO P
OH pseudo- OH
O rotation
HO MeO
(31) (32) (33)

− MeOH

O O
MeO O
P P
OCH2CH2OH OH
OH O

(34) (35)

Scheme 5

systems where pentacoordinated phosphorus may play a 7.6 Catalytic Activation of Organosilicon Reagents by
key role. There are several important biological reactions Nucleophiles15
that are catalyzed by phosphoryl- and nucleotidyl-transfer
enzymes. Many of these are postulated to go through This is one of the most useful applications of organosilicon
‘in-line’ pentacoordinated mechanisms, in which both the reagents in organic chemistry, and ionic fluorides are the most
incoming and departing groups are axial. For example, common catalysts for this purpose. For example, the reduction
the transphosphorylation step of ribonuclease action on a of carbonyl groups is proposed to go through both a 10-Si-5
dinucleotide substrate is suggested to go through a transition and a 12-Si-6 intermediate, as shown in Scheme 6. Many
state that resembles the intermediates in Scheme 5. other reactions, such as the activation of enoxysilanes for the
synthesis of carbon – carbon bonds, are believed to proceed
through hypervalent intermediates. With the knowledge that
7.5 Halosilanes many 10-Si-5 silicates are significantly more reactive than their
8-Si-4 counterparts (Section 6.2), these mechanisms appear
Nucleophilic attack at the silicon atom in halosilanes can
highly plausible.
lead to inversion or retention of configuration, depending on
the nature of the leaving group.81 When the leaving group
is chloride, inversion is the usual course. Since fluoride
is a poorer leaving group, both retention and inversion 7.7 Hypervalent Intermediates in Sulfur Chemistry19,23
are observed with this halide, depending on various other
factors. As usual, the incorporation of rings can alter the usual Evidence for hypervalent intermediates in sulfur chemistry
inversion path; retention is observed in equation (33). is less well established than in phosphorus and silicon chem-
istry. Racemization and reduction of sulfoxides each appear
to go through hypervalent 10-S-4 sulfurane intermediates. In
OH− addition, pathways for the reaction of sulfonium salts with
(33) organometallics involve plausible hypervalent intermediates
Si Si
(Scheme 7). Ligand coupling with retention of configura-
Cl OH
Ph Ph tion is presumed to occur via a sulfurane intermediate

− −
R R
R
R R′2C=O
R3SiH + F− H Si R′2C=O Si R
R
H
F F

−F−

O H
R3Si
R′ R′

Scheme 6

Bu
Me + L−
S S Me Me
Me + BuLi − BuSMe H H
• •
− LiL Me
Me Me Me

H H

Me Me

Scheme 7

(equation 34).83 N P
OO
R RR R
O
S (38)
EtMgBr

PhSO2 PhSO2 8 INTER-LIGAND HYPERVALENT

(34)
INTERACTIONS

The development of the discipline of organometallic

7.8 Transition State Model for Edge Inversion at 8-X-3 chemistry over the past several decades is due in large part to
(X = Group 15 Element) Centers84–86 the way in which transition metals can bind and preorganize
substrates for further reaction. It is quite common for two
The isolation of stable 10-X-3 (X = P, As, Sb) derivatives apparently distinct ligands to engage in reactions with each
(16) led to the idea that this geometry might represent other, or to show structural features indicative of strong
the inversion transition state for trivalent XL3 molecules. interactions, leading to nonclassical structures and bonding
Inversion of these species had been considered to proceed in a arrangements. The undoubted champion in this respect is
similar manner to NH3 ; that is, a vertex pathway whereby the hydride ligand; with its absence of core electrons and a
a vertex is inverted through the center of a tetrahedron 1s valence orbital, hydrogen forms strong bonds with many
via a trigonal planar transition state. In an edge inversion elements. M–H bonds engage in a wide spectrum of secondary
mechanism, the edges of a tetrahedron are inverted via a bonding interactions with other M–L moieties37 (see Agostic
square-planar transition state. These processes are illustrated Bonding; Activation). These may generally be termed Inter-
in Figure 8. Of course, vertex inversion is highly unlikely Ligand Hypervalent Interactions.
when all four substituents are atoms or ligands. However, As long ago as 1988, Crabtree proposed that the silane
when one of the substituents is a nonbonding pair of electrons σ -bond complex [CpMn(CO)2 (HSiFPh2 )] (39) was better
(substituent A in Figure 8), both mechanisms are possible. formulated as a classical silyl hydride.87 This complex displays
Many factors are involved in the choice of one path over a long Si–F bond; Crabtree suggested that this arose from
the other, but the transition state for the edge inversion donation of electron density from the Mn–H bond into the
suitably disposed Si–F σ * orbital (40), with the Si atom
process involves a 3c/4e hypervalent bond with ligands C
adopting a tbp geometry. Thus, instead of viewing the M-Si-H
and D. Calculations have predicted that PH3 and PH2 F invert
moiety as resulting from arrested oxidative addition, addition
via the vertex process, while PHF2 and PF3 favor the edge
is considered to be complete and a secondary back-interaction
pathway. Note that the crossover occurs when two highly
occurs between the resulting silane and hydride ligands.
electronegative substituents are attached. In an elegant study,
(38) was synthesized and its inversion barrier measured by
NMR magnetization transfer experiments. Such a molecule F F
has to invert by the edge mechanism, and calculations based Ph Ph
on this mechanism produced results in good agreement with Si Si
Cp(CO)2Mn Ph Cp(CO)2Mn Ph
the experimental values.
H H
(39) (40)
A
‡
B D
D C
D B A
C
A neutron diffraction structure of the dihydrogen-hydride
B C complex [(EtPh2 P)3 Fe(H)(η2 -H2 )] (41) provided accurate
Vertex inversion process A
positions for the three ligand hydrogen atoms, and revealed
‡ the H2 ligand to be twisted from the expected arrangement
A A
B D so as to bring one of its hydrogen atoms into close
C
D C D proximity with the unique hydride H atom. An attractive
B C interaction appears to occur between the (η2 -H2 ) and H
B A
ligands. This interaction seems to be different in nature
Edge inversion process
to that proposed for representation (40), with little or no
changes evident in the bond lengths of the (η2 -H2 ) and M–H
Figure 8 The vertex and edge inversion processes for 10-X-3 XL3 moieties. Rather is it probably an electrostatic interaction,
(X = Group 15 element) molecules; A is the lone pair; L are B, C, D with the negatively charged hydride H atom being attracted

to the somewhat positive dihydrogen moiety. However, a Cl

distinct type of interaction occurs in trihydride complexes
H
such as [CpIr(PR3 )H3 ]+ . Here it is impossible to discern SiMe2
individual hydride and dihydrogen moieties. Although neutron Cy3P Ha
diffraction has shown the H· · ·H distances in this complex to Ru SiPh3 Nb H
be too long for significant bonding interactions to exist, the Cy3P Hb
1 SiMe2
H NMR spectrum displays massive couplings between the H H
three hydride nuclei: these can be as high as 45 000 Hz. Cl
This phenomenon puzzled chemists for several years, until it (42) (43)
was realized that the effect was quantum mechanical in origin,
with the close hydrogen nuclei exchanging sites by a tunneling
mechanism.88 through a transition state in which a close approach and
The complex [(PCy3 )2 RuH2 (η2 -H2 )(η2 -HSiPh3 )] (42) was interaction of the ligands involved leads to a redistribution
reported to contain two different σ -bond ligands, namely of bonding. Whilst such inter-ligand hypervalent interactions
molecular hydrogen and triphenylsilane.89 Closer inspection have been intimated in reaction schemes for several decades,
revealed, however, that the Si· · ·H ‘nonbonded’ distance it is only recently that they have been observed in the ground
state of transition metal complexes.
was only 6% longer than the Si–H ‘bonded’ one; in other
words the two H atoms trans to the phosphine ligands are
virtually indistinguishable, and both are clearly interacting
with the Si atom. In such a situation, it is more realistic
to consider a single group [H2 SiPh3 ]− acting as a tridentate 9 OTHER HYPERVALENT SPECIES
ligand in this Ru complex, with a 3c/4e bond holding the
H-Si-H moiety together. The ligand is then a pentacoordinate,
9.1 5c/6e Hypervalent Bonding93
hypervalent silicon species, which may be considered an
analog of the trihydrogen anion, [H3 ]− . It is noteworthy in Theoretically, the concept of hypervalent bonding can be
this respect that the recently reported complex [K(18-crown- expanded by adding two centers and two electrons at a time in
6)][H2 SiPh3 ] contains an uncoordinated 10-Si-5 [H2 SiPh3 ]− a linear array. Practically, however, the limit may be reached
ion, in which the hydride ligands occupy the axial sites in a at a 5c/6e system. There are several species of this type known,
tbp structure.90 Analogous behavior has also been reported for such as [Rf –I–F–I–Rf ]− and [F–Xe–F–Xe–F]+ . Pentahalide
the borohydride ligand in a transition metal hydride complex. monoanions like Br5 − are bent and hence do not conform to
Thus, while the two metal centers in the bimetallic ruthenium this 5c/6e model. The addition of two atoms introduces two
complex [(triphos)Ru(H)(BH4 )(H)Ru(triphos)]+ are bridged more σ atomic orbitals to the scheme, which give rise to a
by BH4 − , the analogous iron species is formulated instead total of five MOs. The lowest three of these are occupied in
as [(triphos)Fe(BH6 )Fe(triphos)]+ . The bridging moiety here the hypervalent bonding scheme. The lowest energy MO is
is formally [BH6 ]3− ; a 12-B-6 entity: all B–H distances are bonding with respect to all five atoms; the next is bonding
statistically equivalent, and only a single 1 H resonance is for the first and second and the fourth and fifth atoms, with a
discernable in the hydride region of the NMR spectrum.91,92 node at the central atom; the highest occupied MO is totally
Since the mid-1990s, a wide range of silyl hydride nonbonding with nodes at the second and fourth atoms.
metallocene complexes of Nb and Ta has been reported by
Nikonov, with one example shown in (43). These exhibit short
9.2 Hypervalent Compounds of Period 2
Si–H distances, and show large Si, H coupling constants in
their NMR spectra.36 The Si atom adopts a tbp geometry, with The vast majority of hypervalent species, whether isolable
a ligand such as Cl trans to the interacting hydride. Donation and stable or proposed as reactive intermediates (rather than
of electron density from the M–H bond can then occur into transition states), contain a central atom from period 3 or
the Si–Cl σ * orbital, in the manner described above for (40). below. However, there is indisputable evidence that elements
Example (43), in which an M–H unit simultaneously interacts of period 2 can form species with hypervalent bonds. In fact,
with two Si centers, can also be considered to be held together hydrogen bonding can be considered a form of hypervalent
by a 5c/6e bond (q.v.). bonding for a first period element, in which hydrogen exceeds
What is clear from all these examples is that hydrogen can its ‘duet’. For example, the well-known symmetrical ion
participate in a wide variety of strong secondary interactions [F–H–F]− has a very similar σ -bonding scheme to that
with neighboring ligands in transition metal complexes. IHIs illustrated in Figure 1, except that hydrogen uses an s orbital
constitute a distinct type of nonclassical bonding that is rather than a p orbital,94 and the IHIs described in Section 8
different from other types, such as in σ -bond complexes and require hydrogen to be formally hypervalent.
agostic interactions (see Agostic Bonding). IHIs are important, Nitrogen(V) is an accessible and common oxidation state,
as major catalytic processes like migratory insertions proceed which occurs in such everyday laboratory species as nitric acid

HNO3 and the nitrate ion NO3 − . Nitrogen is precluded from H

forming sp3 dn hybrid orbitals, and this caused early conceptual +
resistance to the idea that these molecules were hypervalent, Me Me
Me Me
with the nonexistence of NF5 being cited as a counterexample.
In fact, it is now clear that the instability of NF5 owes more + O O+
S C− S
to the steric interactions that this pentacoordinate molecule
would suffer:95 the conjugate cation NF4 + is accessible
and has been stabilized in a variety of salts. Furthermore,
the surprisingly unreactive isoelectronic molecule ONF3
has a short nitrogen – oxygen distance, which can only be Ph
categorized as a N=O bond, and hence is clearly a hypervalent
10-C-5
N(V) species. Although nitrogen does not possess valence d
(46) Overall monoanion
orbitals, all these compounds can be easily accommodated
using 3c/4e bonding schemes or resonance structures, as
described in Section 1. such as the organic sulfoxides R2 SO, sufones R2 SO2 , sulfur
The carbon atoms found at the center of a tbp cage, ylides R2 SCR2 , phosphine oxides R3 PO, and phosphorus
examples of which are the theoretical CLi5 96 and the isolated ylides R3 PCR2 . Virtually any molecule or ion for which a
cation C[AuPPh3 ]5 + ,97 might be considered hypervalent on reasonable Lewis structure can be written with multiple bonds
first inspection. However, cage bonding (forming Li–Li and such that the central atom will expand its octet may reasonably
Au–Au linkages) is the key factor in the stability of these be thought of as hypervalent (see Section 1). This includes all
molecules. The first hypervalent fluorine species was reported noble gas molecules and complex ions, as well as high-valent
in 1976 by Ault and Andrews;98 the F3 − ion trapped in halogenated derivatives.
an argon matrix. The mutual exclusion rule for IR and
Raman spectroscopy was convincing evidence for the linear,
symmetrical arrangement of the three fluorine atoms with
a Cs+ counter ion. In 1984, Lee and Martin99 used NMR 10 RELATED ARTICLES
spectroscopy to show that several boron compounds, such
as (44) and (45), were authentic 10-B-5 and 12-B-6 species
Chlorine, Bromine, Iodine, & Astatine: Inorganic Chem-
in solution. The first report of hypervalent 10-C-5 carbon
istry; Coordination Numbers & Geometries; Electronic Struc-
(46) came in 1979 by Forbus and Martin.100 This work was
ture of Main-group Compounds; Molecular Orbital Theory;
expanded in a series of papers in 1993,9,101,102 which presented
Noble Gases: Inorganic Chemistry; Phosphorus: Inorganic
NMR and electrochemical evidence for isolation of the first
Chemistry; Silicon: Inorganic Chemistry; Sulfur: Inorganic
molecule, which is a model for the transition state for an SN 2
Chemistry.
reaction at a tetrahedral carbon center.

F3C CF3 F3C CF3 CF3

O OO CF3 11 REFERENCES
2− 3− +
+N B R +N B N R
R
O 1. J. I. Musher, Angew. Chem., Int. Ed. Engl., 1969, 8, 54.
O O
F3C F3C F3C CF3 2. G. N. Lewis, ‘Valence and the Structure of Atoms and
F3C F3C Molecules’, Chemical Catalog Co., New York, 1923.
10-B-5 12-B-6 3. I. Langmuir, J. Am. Chem. Soc., 1919, 41, 868.
(44) Overall monoanion (45) Overall monoanion 4. A. E. Reed and P. V. Schleyer, J. Am. Chem. Soc., 1990, 112,
1434.
5. W. Thiel and A. A. Voityuk, Int. J. Quantum Chem., 1992, 44,
807.
9.3 Other Species Considered as Hypervalent 6. J. C. Martin, Science, 1983, 221, 509.

Although coordination numbers higher than six were not 7. V. B. Koutecky and J. I. Musher, Theor. Chim. Acta, 1974,
explicitly considered above, certain species, such as the seven- 33, 227.
coordinate 14-I-7 molecule IF7 in a pentagonal bipyramid 8. F. A. Cotton and G. Wilkinson, ‘Advanced Inorganic
geometry, contain a linear F–I–F 3c/4e hypervalent bond. Chemistry’, 5th edn., John Wiley & Sons, New York, 1988,
Hypervalent bonding has also been extended to species that p. 28.
are generally drawn to include double bonds to oxygen or CR2 , 9. T. R. Forbus and J. C. Martin, Heteroat. Chem., 1993, 4, 113.

10. G. Sini, G. Ohanessian, P. C. Hiberty, and S. S. Shaik, J. Am. 34. R. D. Harcourt and T. M. Klapotke, J. Fluor. Chem., 2003,
Chem. Soc., 1990, 112, 1407. 123, 5.
11. D. J. Hajdasz and R. R. Squires, J. Am. Chem. Soc., 1986, 108, 35. A. I. Boldyrev and L. S. Wang, J. Phys. Chem. A, 2001, 105,
3139. 10759.
12. J. Cioslowski and S. T. Mixon, Inorg. Chem., 1993, 32, 3209. 36. G. I. Nikonov, J. Organomet. Chem., 2001, 635, 24.
13. R. J. Gillespie and B. Silvi, Coord. Chem. Rev., 2002, 233, 53. 37. G. S. McGrady and G. Guilera, Chem. Soc. Rev., 2003, 32,
14. C. W. Perkins, J. C. Martin, A. J. Arduengo III, W. Lau, 383.
A. Alegria, and J. K. Kochi, J. Am. Chem. Soc., 1980, 102, 38. V. I. Minkin and R. M. Minyaev, Chem. Rev., 2001, 101,
7753. 1247.
15. R. J. P. Corriu and J. C. Young, in ‘The Silicon-Heteroatom 39. H. J. Frohn and V. V. Bardin, Organometallics, 2001, 20,
Bond’, eds. S. Patai and Z. Rappoport, John Wiley & Sons, 4750.
Chichester, 1991, p. 1 and p. 49. 40. C. E. Holloway and M. Melnik, Main Group Met. Chem.,
16. I. Omae, ‘Organotin Chemistry’, 1st edn., Elsevier, 2000, 23, 1.
Amsterdam, 1989. 41. E. R. T. Tiekink, Rigaku J., 2002, 19, 14.
17. R. R. Holmes, ‘Pentacoordinated Phosphorus’, 1st ed., 42. J. Drabowicz and G. Halaba, Rev. Heteroat. Chem., 2000, 22,
American Chemical Society, Washington, DC, 1980.
1.
18. R. Bohra and H. W. Roesky, Adv. Inorg. Chem., 1984, 28,
43. T. Negoro and S. Oae, Rev. Heteroat. Chem., 1995, 13, 235.
203.
44. A. J. Arduengo III and C. A. Stewart, Chem. Rev., 1994, 94,
19. A. Senning, ed., ‘Sulfur in Organic and Inorganic Chemistry’
1215.
Marcel Dekker, New York, 1982.
45. D. V. Sevenard, A. A. Kolomeitsev, B. Hoge, E. Lork, and
20. G. F. Koser, in ‘The Chemistry of Halides, Pseudo-halides,
G. V. Roschenthaler, J. Am. Chem. Soc., 2003, 125, 12366.
and Azides’, eds. S. Patai and Z. Rappoport, John Wiley &
Sons, Chichester, 1983, p. 721. 46. M. G. Voronkov, V. M. Dyakov, and S. V. Kirpichenko, J.
Organomet. Chem., 1982, 233, 1.
21. K. Seppelt and D. Lentz, Prog. Inorg. Chem., 1982, 29, 167.
47. M. A. H. Laramay and J. G. Verkade, Z. Anorg. Allg. Chem.,
22. R. R. Holmes, Prog. Inorg. Chem., 1984, 32, 119.
1991, 605, 163.
23. D. H. R. Barton ed., ‘Comprehensive Organic Chemistry’,
48. K. M. Kadish, C. Swistak, B. Boisselier-Cocolios, J. M. Barbe,
Pergamon Press, Oxford, 1979.
and R. Guilard, Inorg. Chem., 1986, 25, 4336.
24. E. W. Abel, F. G. A. Stone, and G. Wilkinson eds,
49. A. J. Arduengo III, C. A. Stewart, F. Davidson, D. A. Dixon,
‘Comprehensive Organometallic Chemistry II’, Pergamon
J. Y. Becker, S. A. Culley, and M. B. Mizen, J. Am. Chem.
Press, Oxford, 1995.
Soc., 1987, 109, 627.
25. G. Wilkinson ed., ‘Comprehensive Organometallic Chem-
50. T. J. Atkins and J. E. Richman, Tetrahedron Lett., 1978, 5149.
istry’, Pergamon Press, Oxford, 1982.
51. L. Khriachtchev, M. Pettersson, N. Runeberg, J. Lundell, and
26. J. A. McCleverty and T. J. Meyer eds, ‘Comprehensive
M. Rasanen, Nature, 2000, 406, 874.
Coordination Chemistry II’, Elsevier, Amsterdam, 2003.
52. J. Emsley and D. Hall, ‘The Chemistry of Phosphorus’, John
27. G. Wilkinson, ed., ‘Comprehensive Coordination Chemistry’,
Wiley & Sons, New York, 1976.
Pergamon Press, Oxford, 1987.
53. D. E. C. Corbridge, ‘Phosphorus’, 3rd edn., Elsevier,
28. N. N. Greenwood and A. Earnshaw, ‘Chemistry of the
Amsterdam, 1985.
Elements’, Pergamon, Oxford, 1984.
54. R. J. Gillespie and I. Hargittai, ‘The VSEPR Model of
29. T. Wirth, Hypervalent Iodine Chemistry – Modern Devel-
opments in Organic Synthesis – Introduction and General Molecular Geometry’, Alleyn and Bacon, Boston, MA, 1991.
Aspects, in ‘Hypervalent Iodine Chemistry: Modern Develop- 55. K. Nakamoto, ‘Infrared and Raman Spectra of Inorganic and
ments in Organic Synthesis’; Top. Curr. Chem., 2002, 224, Coordination Compounds’, 4th edn., John Wiley & Sons, New
1. York, 1986.
30. H. Tohma and Y. Kita, Synthetic Applications (total synthesis 56. K. O. Christe and W. W. Wilson, Inorg. Chem., 1989, 28,
and natural product synthesis), in ‘Hypervalent Iodine 3275.
Chemistry: Modern Developments in Organic Synthesis’; Top. 57. H. Beckers, J. Breidung, H. Burger, R. Kuna, A. Rahner,
Curr. Chem., 2002, 224, 209. W. Schneider, and W. Thiel, J. Chem. Phys., 1990, 93, 4603.
31. T. Kitamura and Y. Fujiwara, Org. Prep. Proced. Int., 1997, 58. J. G. Verkade and L. D. Quin eds, ‘Phosphorus-31 NMR
29, 409. Spectroscopy in Stereochemical Analysis’, VCH, Deerfield
32. D. Uraguchi, T. Ooi, and K. Maruoka, J. Synth. Org. Chem., Beach, 1987.
Jpn., 2000, 58, 14. 59. D. Christen, J. Kadel, A. Liedtke, R. Minkwitz, and
33. M. Nakajima, J. Synth. Org. Chem., Jpn., 2000, 58, 839. H. Oberhammer, J. Phys. Chem., 1989, 93, 6672.

60. R. H. Herber, ed., ‘Chemical Mossbauer Spectroscopy’, 83. S. Oae and Y. Uchida, Acc. Chem. Res., 1991, 24, 202.
Plenum, New York, 1984. 84. A. J. Arduengo III and D. A. Dixon, in ‘Heteroatom
61. A. H. Cowley, M. Lattman, and M. L. Walker, J. Am. Chem. Chemistry: ICHAC-2’, ed. E. Block, VCH: New York, 1990,
Soc., 1979, 101, 4074. p. 47.
62. R. W. Shaw, T. X. Carroll, and T. D. Thomas, J. Am. Chem. 85. A. J. Arduengo III, D. A. Dixon, and D. C. Roe, J. Am. Chem.
Soc., 1973, 95, 5870. Soc., 1986, 108, 6821.
63. S. Trippet, Pure Appl. Chem., 1974, 40, 595. 86. D. A. Dixon, A. J. Arduengo, and T. Fukunaga, J. Am. Chem.
64. J. A. Deiters, R. R. Holmes, and J. M. Holmes, J. Am. Chem. Soc., 1986, 108, 2461.
Soc., 1988, 110, 7672. 87. R. H. Crabtree and D. G. Hamilton, Adv. Organomet. Chem.,
65. R. Hoffmann, J. M. Howell, and E. L. Muetterties, J. Am. 1988, 28, 299.
Chem. Soc., 1972, 94, 3047. 88. F. Maseras, A. Lledos, E. Clot, and O. Eisenstein, Chem. Rev.,
66. M. M. L. Chen and R. Hoffmann, J. Am. Chem. Soc., 1976, 2000, 100, 601.
98, 1647. 89. K. Hussein, C. J. Marsden, J. C. Barthelat, V. Rodriguez,
67. H. Oberhammer, J. Grobe, and D. Le Van, Inorg. Chem., 1982, S. Conejero, S. Sabo-Etienne, B. Donnadieu, and B. Chaudret,
21, 275. Chem. Commun., 1999, 1315.
68. R. S. Berry, J. Chem. Phys., 1960, 32, 933. 90. M. J. Bearpark, G. S. McGrady, P. D. Prince, and J. W. Steed,
J. Am. Chem. Soc., 2001, 123, 7736.
69. L. D. Martin, E. F. Perozzi, and J. C. Martin, J. Am. Chem.
Soc., 1979, 101, 3595. 91. G. S. McGrady, G. Guilera, J. W. Steed, and N. Kaltsoyannis,
New J. Chem., 2004, 28, 444.
70. D. S. Brown, F. W. Einstein, and D. G. Tuck, Inorg. Chem.,
1969, 8, 14. 92. A. C. Hillier, H. Jacobsen, D. Gusev, H. W. Schmalle, and
H. Berke, Inorg. Chem., 2001, 40, 6334.
71. W. Bubenheim, G. Frenzen, and U. Muller, Acta Crystallogr.
Sect. C: Cryst. Struct. Commun., 1995, 51, 1120. 93. D. A. Dixon, A. J. Arduengo III, and W. B. Farnham, Inorg.
Chem., 1989, 28, 4589.
72. J. Taraba and Z. Zak, Inorg. Chem., 2003, 42, 3591.
94. J. Emsley, Chem. Soc. Rev., 1980, 9, 91.
73. W. C. Smith, Angew. Chem., Int. Ed. Engl., 1962, 1, 467.
95. K. O. Christe, W. W. Wilson, G. J. Schrobilgen, R. V.
74. D. B. Dess and J. C. Martin, J. Organomet. Chem., 1983, 48,
Chirakal, and G. A. Olah, Inorg. Chem., 1988, 27, 789.
4155.
96. P. V. Schleyer, E. U. Wurthwein, E. Kaufmann, T. Clark,
75. R. M. Moriarty and O. Prakash, Acc. Chem. Res., 1986, 19,
and J. A. Pople, J. Am. Chem. Soc., 1983, 105,
244.
5930.
76. T. Wirth, Oxidations and rearrangements in ‘Hypervalent
97. F. Scherbaum, A. Grohmann, G. Muller, and H. Schmidbaur,
Iodine Chemistry: Modern Developments in Organic
Angew. Chem., Int. Ed. Engl., 1989, 28, 463.
Synthesis’; Top. Curr. Chem., 2002, 224, 185.
98. B. S. Ault and L. Andrews, Inorg. Chem., 1977, 16, 2024.
77. M. Lattman, B. N. Anand, D. R. Garrett, and M. A. Whitener,
Inorg. Chim. Acta, 1983, 76, L139. 99. D. Y. Lee and J. C. Martin, J. Am. Chem. Soc., 1984, 106,
5745.
78. E. A. V. Ebsworth, J. H. Holloway, N. J. Pilkington, and
D. W. H. Rankin, Angew. Chem., Int. Ed. Engl., 1984, 23, 630. 100. T. R. Forbus and J. C. Martin, J. Am. Chem. Soc., 1979, 101,
5057.
79. A. J. Arduengo III, M. Lattman, H. V. R. Dias, J. C. Cala-
brese, and M. Kline, J. Am. Chem. Soc., 1991, 113, 1799. 101. T. R. Forbus and J. C. Martin, Heteroat. Chem., 1993, 4,
129.
80. A. J. Arduengo III, H. V. R. Dias, and J. C. Calabrese, J. Am.
Chem. Soc., 1991, 113, 7071. 102. T. R. Forbus, J. L. Kahl, L. R. Faulkner, and J. C. Martin,
Heteroat. Chem., 1993, 4, 137.
81. R. R. Holmes, Chem. Rev., 1990, 90, 17.
82. F. H. Westheimer, Acc. Chem. Res., 1968, 1, 70.

Hipervalenta Articol
No ratings yet
Hipervalenta Articol
10 pages
Hypervalency in Main Group Chemistry
No ratings yet
Hypervalency in Main Group Chemistry
57 pages
Hypervalence vs. Octet Rule Analysis
100% (1)
Hypervalence vs. Octet Rule Analysis
2 pages
Lectures P Block Elements 3 Hypervalency
No ratings yet
Lectures P Block Elements 3 Hypervalency
26 pages
Charge Density in Main Group Chemistry
No ratings yet
Charge Density in Main Group Chemistry
25 pages
Understanding Hypervalency in Molecules
No ratings yet
Understanding Hypervalency in Molecules
26 pages
3 - JEE - Chemistry - Chemical Bonding - Covalent Bond
No ratings yet
3 - JEE - Chemistry - Chemical Bonding - Covalent Bond
8 pages
Exceptions to the Octet Rule Explained
No ratings yet
Exceptions to the Octet Rule Explained
14 pages
Chapter04 - Chemical Bonding Typ PDF
No ratings yet
Chapter04 - Chemical Bonding Typ PDF
73 pages
Chemical Bonding
No ratings yet
Chemical Bonding
38 pages
Understanding Chemical Bonding Concepts
No ratings yet
Understanding Chemical Bonding Concepts
84 pages
Advanced Chemistry: Octet Rule Exceptions
No ratings yet
Advanced Chemistry: Octet Rule Exceptions
4 pages
Chemical Bonding
No ratings yet
Chemical Bonding
26 pages
Unit 4
No ratings yet
Unit 4
30 pages
Neet - Chemistry - Chemical Bonding
No ratings yet
Neet - Chemistry - Chemical Bonding
87 pages
Understanding Covalent Compounds
No ratings yet
Understanding Covalent Compounds
9 pages
Chemical Bonding1
No ratings yet
Chemical Bonding1
69 pages
Understanding Chemical Bonding Basics
No ratings yet
Understanding Chemical Bonding Basics
21 pages
Understanding Covalent Compounds
No ratings yet
Understanding Covalent Compounds
19 pages
Understanding Chemical Bonding Concepts
100% (3)
Understanding Chemical Bonding Concepts
71 pages
CH Bonding
No ratings yet
CH Bonding
15 pages
Understanding Chemical Bonding Types
No ratings yet
Understanding Chemical Bonding Types
9 pages
Basic Inorganic Chemistry (IIT JAM)
No ratings yet
Basic Inorganic Chemistry (IIT JAM)
22 pages
Covalentbonds 200409121602
No ratings yet
Covalentbonds 200409121602
50 pages
Chemical Bonding 1
No ratings yet
Chemical Bonding 1
25 pages
AC-Unit-1-Chemical Bondings and Catalysis - English
No ratings yet
AC-Unit-1-Chemical Bondings and Catalysis - English
23 pages
Chemical Bonding and Molecular Structure
No ratings yet
Chemical Bonding and Molecular Structure
146 pages
Chemical Bonding
No ratings yet
Chemical Bonding
33 pages
Covalent Bonds and Molecular Geometry Module
No ratings yet
Covalent Bonds and Molecular Geometry Module
16 pages
Gen Chem 1 Q2 Module 3
100% (2)
Gen Chem 1 Q2 Module 3
14 pages
Covalent Bonding Explained
100% (1)
Covalent Bonding Explained
109 pages
Chemistry Basics: Bonds & Molecules
No ratings yet
Chemistry Basics: Bonds & Molecules
31 pages
Chemical Bonding Overview
No ratings yet
Chemical Bonding Overview
13 pages
Understanding Chemical Bonding Types
No ratings yet
Understanding Chemical Bonding Types
16 pages
Understanding Chemical Bonding Basics
No ratings yet
Understanding Chemical Bonding Basics
40 pages
Electronic Theory of Valency and Bonding Powerpresentation
No ratings yet
Electronic Theory of Valency and Bonding Powerpresentation
61 pages
NEET Revision Notes For Chemistry Chemical Bonding and Molecular Structure
100% (1)
NEET Revision Notes For Chemistry Chemical Bonding and Molecular Structure
21 pages
Covalent Bonding and Electronegativity
No ratings yet
Covalent Bonding and Electronegativity
64 pages
Understanding Covalent Bonds and Properties
No ratings yet
Understanding Covalent Bonds and Properties
7 pages
Limitations of Octet Theory Explained
No ratings yet
Limitations of Octet Theory Explained
8 pages
Advanced Chemistry Concepts
No ratings yet
Advanced Chemistry Concepts
44 pages
Chemical Bonding & Structure Guide
No ratings yet
Chemical Bonding & Structure Guide
47 pages
Chemistry for Students
No ratings yet
Chemistry for Students
51 pages
Oxidation Numbers and Bonding Types
No ratings yet
Oxidation Numbers and Bonding Types
33 pages
CHE 1261 - Chemical Bonding-VU - FH
No ratings yet
CHE 1261 - Chemical Bonding-VU - FH
37 pages
Chemical Bonding Uss
No ratings yet
Chemical Bonding Uss
8 pages
Chemical Bonding - 8881390557
No ratings yet
Chemical Bonding - 8881390557
87 pages
Understanding Covalent Bond Formation
No ratings yet
Understanding Covalent Bond Formation
54 pages
Covalent Bonds and Molecular Geometry
No ratings yet
Covalent Bonds and Molecular Geometry
14 pages
Ionic and Covalent Bonding Explained
No ratings yet
Ionic and Covalent Bonding Explained
11 pages
Chemical Bonding and Molecular Structure
No ratings yet
Chemical Bonding and Molecular Structure
47 pages
Chemical Bonding 1
No ratings yet
Chemical Bonding 1
139 pages
Chemical Bonding Concepts in Inorganic Chemistry
No ratings yet
Chemical Bonding Concepts in Inorganic Chemistry
145 pages
Chemical Bonding Session Notes
No ratings yet
Chemical Bonding Session Notes
162 pages
Chemical Bond
No ratings yet
Chemical Bond
27 pages
Introduction to Chemical Bonds
No ratings yet
Introduction to Chemical Bonds
24 pages
Chemical Bonding and Molecular Structure
100% (4)
Chemical Bonding and Molecular Structure
30 pages
Diet and Dental Caries Prevention Guide
No ratings yet
Diet and Dental Caries Prevention Guide
11 pages
WJG 12 3359
No ratings yet
WJG 12 3359
9 pages
Wang 2019
No ratings yet
Wang 2019
38 pages
10.1016@B978 0 444 64046 8.00157 9
No ratings yet
10.1016@B978 0 444 64046 8.00157 9
8 pages
Measuring Radon Levels in Homes
No ratings yet
Measuring Radon Levels in Homes
15 pages
The Science o F The Total Environment, 45 (1985) 351 - 356
No ratings yet
The Science o F The Total Environment, 45 (1985) 351 - 356
6 pages
Radon Exposure and Lung Cancer Risk in Denmark
No ratings yet
Radon Exposure and Lung Cancer Risk in Denmark
7 pages
Cobalamin's Role in Subacute Combined Degeneration
No ratings yet
Cobalamin's Role in Subacute Combined Degeneration
17 pages
Cost-Benefit Analyses of Radon Mitigation Projects: Mads Lyngby Petersen, Thommy Larsen
No ratings yet
Cost-Benefit Analyses of Radon Mitigation Projects: Mads Lyngby Petersen, Thommy Larsen
8 pages
Didi
No ratings yet
Didi
12 pages
Global Residential Radon Levels Analysis
No ratings yet
Global Residential Radon Levels Analysis
12 pages
Vitamin B12's Impact on Birth Defects
No ratings yet
Vitamin B12's Impact on Birth Defects
7 pages
Review Article Electrochemistry and Catalytic Properties of Vitamin B Derivatives in Nonaqueous Media
No ratings yet
Review Article Electrochemistry and Catalytic Properties of Vitamin B Derivatives in Nonaqueous Media
7 pages
Gangrene and Solanin Poisoning in Horses
No ratings yet
Gangrene and Solanin Poisoning in Horses
2 pages
The Final Seminar
No ratings yet
The Final Seminar
45 pages
Emission Spectra of Copper and Barium
No ratings yet
Emission Spectra of Copper and Barium
6 pages
Stoichiometry: Atomic & Molecular Mass Guide
No ratings yet
Stoichiometry: Atomic & Molecular Mass Guide
3 pages
CHM307
No ratings yet
CHM307
2 pages
Periodicity of Elements
No ratings yet
Periodicity of Elements
29 pages
Covalent Bonding and Hybridization Explained
No ratings yet
Covalent Bonding and Hybridization Explained
17 pages
How Are Electrons Arranged in The Atom?
No ratings yet
How Are Electrons Arranged in The Atom?
24 pages
Solutions Manual for Chemical Principles
100% (76)
Solutions Manual for Chemical Principles
47 pages
0structure of Atom Class 11th Notes
No ratings yet
0structure of Atom Class 11th Notes
19 pages
Physical Chemistry Vol III Gurtu Ebook Complete PDF Edition
100% (6)
Physical Chemistry Vol III Gurtu Ebook Complete PDF Edition
100 pages
Grade 11 Physical Science Midterm Exam
83% (6)
Grade 11 Physical Science Midterm Exam
2 pages
Millikan Oil Drop Experiment Explained
No ratings yet
Millikan Oil Drop Experiment Explained
2 pages
Periodic Table and Element Properties
No ratings yet
Periodic Table and Element Properties
32 pages
Periodic Table Elements and Properties Quiz
No ratings yet
Periodic Table Elements and Properties Quiz
9 pages
BPSC Mineral Development Officermdoexam Gs Question Paper Hindi
No ratings yet
BPSC Mineral Development Officermdoexam Gs Question Paper Hindi
14 pages
Doping Mechanisms in Organic Semiconductors
No ratings yet
Doping Mechanisms in Organic Semiconductors
23 pages
Electrochemistry and Quantum Mechanics Questions
No ratings yet
Electrochemistry and Quantum Mechanics Questions
28 pages
Single Bonds
No ratings yet
Single Bonds
4 pages
Atomic Structure Lesson Plan
No ratings yet
Atomic Structure Lesson Plan
4 pages
Density Functional Theory Advances
No ratings yet
Density Functional Theory Advances
8 pages
Molecular Geometry - Tuesday
No ratings yet
Molecular Geometry - Tuesday
45 pages
Bridge Course JEE QP
No ratings yet
Bridge Course JEE QP
12 pages
Elements of Geochemistry - Lesson 2 - Cosmic Abundance
No ratings yet
Elements of Geochemistry - Lesson 2 - Cosmic Abundance
12 pages
Chemistry For Engineers 1 Energy Topic 04 Nuclear Chemistry 2
No ratings yet
Chemistry For Engineers 1 Energy Topic 04 Nuclear Chemistry 2
13 pages
Chemistry Form 1 Term 2 Scheme of Work
No ratings yet
Chemistry Form 1 Term 2 Scheme of Work
13 pages
Hsslive - in - Xi - Chem - 3. Classification of Elements
No ratings yet
Hsslive - in - Xi - Chem - 3. Classification of Elements
8 pages
Nuclear Chemistry Basics
No ratings yet
Nuclear Chemistry Basics
30 pages
Optical Properties of Solids BY Mark Fox: Chapter 2: Classical Propagation
No ratings yet
Optical Properties of Solids BY Mark Fox: Chapter 2: Classical Propagation
13 pages
Grade 9 - Chemistry - Ionic Bonding
No ratings yet
Grade 9 - Chemistry - Ionic Bonding
23 pages
Assignment 30-10-2025 Submit
No ratings yet
Assignment 30-10-2025 Submit
1 page

Hypervalent Compounds: G. Sean Mcgrady & Jonathan W. Steed

Uploaded by

Hypervalent Compounds: G. Sean Mcgrady & Jonathan W. Steed

Uploaded by

Hypervalent Compounds ICl3 , and SeCl4 were first reported almost two centuries

ago, appropriate models to describe the bonding in these

ion features an atom surrounded by a total of more than •

expanded octet is a result of increased valence or bond • •

count electrons. (5)

to describing the bonding in PF5 is to expand the valence z

geometry but also in pseudo-tbp structures in which one or F F

molecule. Only in the case of an octahedron or octahedral F Cl •• F Xe F

Substituent site preferences in a tbp are based on (what

F3C CF3 t-Bu

3.3.4 Central Atom Charge

4.2 Vibrational Spectroscopy

been used to obtain information on the electronic structures of F CF3 CF3 F

Figure 5 Trifluoromethyl derivatives of PF5

5 PENTACOORDINATE AND RELATED

(23) (24) Figure 6 The Berry pseudorotation process

RCH2OH has been recently reviewed.29–31,76

Scheme 2 R 1R2CO + 2AcOH + O

t-Bu t-Bu t-Bu

PEt3 PEt3 at the central atom of a tetracoordinated molecule or ion.

PhSO2 PhSO2 8 INTER-LIGAND HYPERVALENT

The development of the discipline of organometallic

to the somewhat positive dihydrogen moiety. However, a Cl

HNO3 and the nitrate ion NO3 − . Nitrogen is precluded from H

F3C CF3 F3C CF3 CF3

You might also like