Characterization of
Organometallic Compounds
Peter H.M. Budzelaar
Characterization of organometallics
Main characterization methods:
Xray diffraction (static) structure bonding
NMR structure en dynamic behaviour
EA assessment of purity
(calculations)
Less frequently used:
IR
MS
EPR
Not used much:
GC
LC
Characterization: Xray and NMR
X-ray diffraction
Need well-defined single crystal(s)
preferably about 0.1-0.2 mm in each dimension
may be cut from a larger crystal
needles and leaflets are a problem
tricks for handling highly air-sensitive compounds
A measurement takes about a day
on a modern diffractometer
Solution and refinement take a few hours
some details may require special attention
Some compounds will never yield a good crystal structure !
Characterization: Xray and NMR
X-ray diffraction
X-ray diffraction actually measures electron density
positions of heavy atoms easy to find
H atoms often not found at all
if H atoms are found, bond lengths will not be accurate
it may be hard to distinguish between C/N/O, or e.g. Rh/Ag
X-ray diffraction measures an average in space and in time
in case of disorder, you will see a superposition of molecules
hard to distinguish between dynamic and static disorder
what is the time-scale of X-ray diffraction?
X-ray diffraction says nothing about purity of a sample !
it only says something about the one crystal you measured
"crystal picking"
Don't always "believe" published X-ray structures, stay critical
Characterization: Xray and NMR
Too weird to be true ?
Electrochemical Preparation of Platinum Icocyanide Clusters Containing
Chelating Diphosphines. An Unprecedented Trinuclear Platinum Complex
Involving a Coordinatively Unsaturated Metal Center, [{Pt(diphosphine)
(isocyanide)}2Pt](PF6)2
Tanase, T.; Ukaji, H.; Kudo, Y.; Ohno, M.; Kobayashi, K.; Yamamoto, Y.
Organometallics 1994, 13, 1374
Characterization: Xray and NMR
Indeed !
Clusters [{Pt(diphosphine)(isocyanide)}2Pt]2+ Recharacterized as
[{Pt(diphosphine)(isocyanide)}2Hg]2+
Tanase, T.; Yamamoto, Y.; Puddephatt, R.J.
Organometallics 1996, 15, 1502
Characterization: Xray and NMR
NMR spectroscopy
NMR of organometallic Compounds:
The organic groups (alkyl/aryl)
The other ligands
The metal
Coupling with heteronuclei
Fluxionality (dynamical behaviour)
Characterization: Xray and NMR
The organic groups (alkyl/aryl)
Alkyl groups
at main group metals:
shift to high field (compared to a H or CH3 substituent):
0-4 ppm in 1H, 0-15 ppm in 13C
the metal is a -donor!
how much? Look at difference in electronegativity!
at transition metals:
larger high-field shift for metals with a partially filled d shell
Aryl groups
usually low-field shift of ortho H, ipso and ortho C
Hydrides
extreme high-field shift (up to 100 ppm)
for metals with a partially filled d shell
X
ipso
ortho
meta
para
Characterization: Xray and NMR
The other ligands
Non-"4n+2" systems usually become more aromatic,
as if they had obtained the charge required by "4n+2":
++
--
Arenes become less aromatic and sometimes more localized
N
Rh
N
Characterization: Xray and NMR
The other ligands
Olefins shift to higher field (metallacyclopropane character!)
free
ethene
coordinated
ethene
cyclopropane
5.2
1-3
0.2
122
40-90
-3
approximate
bond lengths:
1.34
1
13
10
1.41
1.50
Characterization: Xray and NMR
The other ligands
Terminal CO ligands
C 170-240 ppm
13
11
Characterization: Xray and NMR
The metal
Many metal nuclei have (an isotope with) non-zero spin
Metal NMR?
Coupling
Line broadening
Metal NMR is often doable but not often useful
12
Characterization: Xray and NMR
Coupling to heteronuclei
(metal and others)
Expected pattern for 1H and 13C signals for an M-CH3 group:
M is NMR-inactive
M has S = 1/2
M has S = 3/2
M has 30% S = 1/2,
rest NMR-inactive
13
Characterization: Xray and NMR
Fluxionality
(dynamical behaviour)
The NMR time scale is seconds, we look at differences in peak
positions of the order of Hz to hundreds of Hz.
If nuclei move much more slowly, we see separate peaks.
If nuclei move much faster, we see averaged peaks.
In the intermediate region we see "coalescence".
From the changes in the NMR spectrum you can extract both
qualitative and quantitative information about the movement
(reaction).
14
Characterization: Xray and NMR
Fluxionality
(dynamical behaviour)
High temperature
Fast exchange
"fast-exchange limit"
2
T
G RTcoal 22.96 ln coal
kcoal
Coalescence
Low temperature
Slow exchange
"slow-exchange limit"
15
Characterization: Xray and NMR
Fluxionality
(dynamical behaviour)
SiMe2F
FMe2Si
SiMe2F
FMe2Si
SiMe2F
SiMe2F
F
Me2Si
SiMe2
Me2Si
SiMe2
F
16
Me2
Si F
Si F
Me2
Characterization: Xray and NMR
