PHYSICAL METHODS

NMR NMR cont.

● Nuclear spin (I) → depends on Z and isotopic mass ○ Some nuclei have small values for Q and can give high
● Magnetic moment (μ) → μ = γħ[I(IH)]½ (dependant on spin) resolution spectra (if the molecule has formal Td and Oh
● Magnetogyric ratio (γ) → ratio of the magnetic momentum in a particle symmetry there is no relaxation)
to its angular momentum ○ Relaxation of Cl is so fast that there is no coupling
○ Has a sign (+/-) ● Chemical equivalence → the nuclei experience the same electronic
○ Is a fundamental property of an isotope environment and thus have the same chemical shift
● Magnetic quantum number (ml) = 2nI+1 (n = number of equivalent ● Magnetic equivalence → the nuclei are chemically equivalent and also
nuclei) have identical coupling constants with all other nuclei in the molecule,
○ For a given spin state there are a defined number of energy resulting in identical splitting patterns in the NMR spectrum
level available
● Satellites → multiplicity of the satellites and central resonance must be
○ Selection rule: ∆ml = ±1
the same
For 11H (I=½): ● Factors influencing coupling constants
- When E=0 (no field) all states are
degenerate 1. One bond M-L coupling constants: effect
- When E ≠ 0 degeneracy is lifted of trans-ligand

- Magnitude of J increase as the strength

of the M-P bond increases
- P competes with the trans ligand
2. Two bond coupling across metal centres
- 2-bond trans-coupling > 2-bond
cis-coupling
● Receptivity → relative detectability of a particular element (γ3NI(IH) (N = 3. Effect of oxidation state
natural abundance)) - The J-value increases as the oxidation
● Larmor frequency state of the metal centre decreases (becomes more
○ Energy levels: E = mlγBħ; ∆E = γBħ; E = hv electron rich)
EXAMPLE: 400MHz spectrometer driven by magnetic field
- γ = 108 T-1s-1 (for 31P) 4. Effect of the magnetogyric ratio
- B = 9T - J ∝ γ of coupling nuclei if all factors remain the same
- ∆E = γBħ → 108 T-1s-1 x 9T x 1.05*10-34Js = 9.45*10-26J - γ1/γ2 ≃ J1/J2
- Substitute into E = hv → v = (9.45*10-26J)/(6.626*10-34Js) → v = ● CNMR spectra in metal complexes
142619981s-1 = 142619981Hz = 142.9 MHz (operating frequency for 31P ○ Chemical shifts can be similar to those of free species
on a 400MHz spectrometer)
- ∆E ∝ γ → γE/γH x spectrometer frequency = larmor frequency
- ∆E ∝ B → higher field spectrometry can provide extra sensitivity
● Relaxation → non-radiative relaxation to ground state
○ T1 (spin-lattice relaxation): dissipation of excited state
energy to the surroundings (large T1 means slow relaxation)
○ T2 (spin-spin relaxation): dissipation of excited state energy
to other spins
○ Tx in units of s (1/Tx is a rate; s-1)
○ T1 ≽ T2 but in high resolution NMR spectroscopy, can
assume T1 = T2
● Heisenberg uncertainty → ∆E∆t = ħ/2 (∆E = uncertainty in energy of the
resonance, ∆t = excited state lifetime)
○ Short lifetime, small ∆t
○ If ∆t is small there is a large ∆E (if an excited state relaxes ○ Metal carbonyls (M-CO) → terminal CO (δ1800-220ppm),
too quickly, there is significant uncertainty in the energy of bridging CO (δ<280 ppm); no C-H (no decoupling, no
the transition and the spectra become broad → lost polarisation transfer, weak signals); low abundance; long
resolution and chemical shift information) relaxation times
○ Longer lifetime (large ∆t, small ∆E) provides high energy ○ Effect of carbon hybridisation → the greater the %
spectra (e.g. paramagnetic species) s-character, the greater the J-value (2s penetrates the
● Quadrupolar nuclei → nuclei with I ≽ 1 nucleus better than 2p)
○ Has a prolate charge distribution ● Dynamic processes → timescale ≃ 1/(frequency of
○ For a molecule with high symmetry (formal Td and Oh) experiment) (NMR ≃ 10-6s, IR = 10-12s
around the quadrupolar nucleus, there is no effect on ○ Individual species involved in exchange can be seen if rate
relaxation of exchange is less than the experimental timescale
○ Where lower symmetry is found, there is an electric field For a molecule that is stereochemically non-rigid (Berry-pseudo
gradient at the nucleus (promotes fast relaxation) rotation):
Rate of quadrupolar relaxation (RQR) - -1000C > T > -1120C (T= coalescence temperature)
- coalescence temperature can be used to obtain ∆G‡

- qx = electric field gradient (0 for Td and Oh symmetry); η = asymmetry of

electric field; Q = quadrupole moment; τc = reflects molecular motion
(correlation time); T1 = quadrupolar relaxation time

EPR (electron paramagnetic resonance)

● Uses spin of unpaired electron (I = +/-½)
● Quantum spin number Ms (selection rule ∆ms = ±1)
● hv = ∆E = gB0μB (g = g-value, B0 = external magnetic field at resonance, μB = Bohr magneton)
● g-value (EPR equivalent of chemical shift) → the position of the resonance absorption signal (measured as the magnetic field, B0, at a fixed frequency, ν) gives the
g-value (for a free electron, g = 2.00232)
○ Heavy atoms with significant spin-orbit coupling can cause substantial shifts in the g-value from the free electron value
● Bohr magneton (μB) → μB = -γeħ (∆E ∝ γ) (e = elementary charge)
● Hyperfine coupling (a) (EPR equivalent of J-value) → parameter that describes the interaction between the magnetic moments of an unpaired electron and a
nearby nucleus
○ Energy of electron spin state is modified to → E = gμBB0Ms + aMsml
○ Magnitude of a can give information about the HOMO (unpaired electron) → a reflects the electron density at the position of the nucleus (a larger
hyperfine coupling constant indicates a higher probability of finding the unpaired electron near the nucleus)
 ○ a∝γ
● Timescale of EPR experiment is much faster than NMR so rapid relaxation of quadrupolar nuclei is not a problem (resolved coupling to quadrupolar nuclei)

Strategy for NMR Strategy for EPR

1. What nucleus am I looking at? 1. Where is the unpaired electron?

2. How many chemically distinct nuclei are there, of what type?

● This gives the number of distinct resonances we expect in the NMR

3. Look at each resonances in turn

4. Which nuclei might it couple with? (what I see not what I am) 4. Which nuclei might it couple with? (what I see not what I am)
● I = 0 (NMR silent) – NO ● The electron couples with nuclei it contacts and surrounding nuclei
● I = ½ (nuclear dipole) –YES ● I = 0 (NMR silent) – NO
● I > 1 (nuclear quadrupole) – MAYBE ● I = ½ (nuclear dipole) –YES
○ High symmetry environment (Td and Oh) ● I > 1 (nuclear quadrupole) – YES
○ Low value of nuclear quadrupole moment ● Spin dilute nuclei – COMPLEX
○ If both are true, than PROBABLY ○ Look at each isotopologue in turn, then superimpose
● Decoupled nuclei – NO ○ Even if I=0, 2nI+1=1 (satellites)
● Spin dilute nuclei – COMPLEX
○ Look at each isotopologue in turn, then superimpose
○ If I=0, 2nI+1=1 (satellites when coupling to Pt, ect.)

5. Look at each predicted coupling in turn 5. Look at each predicted coupling in turn
● Multiplicity/intensity (2nI+1, Pascals triangle) ● Multiplicity/intensity (2nI+1, Pascals triangle)
○ When coupling to a single nucleus, each line has the same ○ When coupling to a single nucleus, each line has the same
intensity intensity
○ When coupling to more than one nucleus, the relative ○ When coupling to more than one nucleus, the relative
intensity of each line is determined by the number of intensity of each line is determined by the number of
interacting nuclei (I=½ use pascal's triangle) interacting nuclei (I=½ use pascal's triangle)
● Magnitude (number of bonds, angles, magnetogyric ratio) ● Magnitude (probability density function, magnetogyric ratio)

6. Tree diagram 6. Tree diagram

● Draw out for each resonances, starting from a singlet ● Draw out for each resonances, starting from a singlet
● Apply the coupling to the singlet, successively and in decreasing size ● Apply the coupling to the singlet, successively and in decreasing size
order order of a (decreasing magnetogyric ratio)

7. Repeat the process for all of the resonances of the nuclei you are looking at 7. Repeat the process for all of the resonances of the nuclei you are looking at

8. Consider relative integral values when you draw the different resonances next 8. Consider relative integral values when you draw the different resonances next
to each other to each other

Vibrational Spectroscopy
● A linear molecule with N atoms has 3N – 5 vibrational modes and a non-linear molecule has 3N – 6
such modes
● For infrared spectroscopy, the vibration must lead to a change in dipole moment (vibrations have the
same irreducible representation as one of the translational modes, Tx, Ty, Tz)
● For Raman spectroscopy, the vibration must lead to a change in polarisability (vibrations have the
same irreducible representation as one of the quadratic functions of the point group; the d-orbitals)
● Where a molecule has an inversion centre, then the Rule of Mutual Exclusion applies and vibrational
modes are either infrared or Raman active
● In non-centrosymmetric point groups, vibrational modes may be Raman and IR active

INTEGRATED ANALYSIS
 ● IR spectroscopy → Intensities of an IR absorption relates to the change in dipole moments that accompanies the vibration
Mass Spectrometry
● Nitrogen rule → a molecule with an odd nominal mass has an odd number of nitrogen atoms
● Degrees of unsaturations/rings = (2C+2+N–H–X)/2

(1) Identify A+2 elements, (2) Correct for peak contributions to M+1 peak, (3) Calculate the number of C atoms

Determine the number of carbon atoms → n (carbon atoms) = M+1 peak (when M peak is 100%) / 1.1% (the rest is contributions from other atoms

CHN Analysis → (nominal mass x CHN percentage as decimal) / molar mass of specific atom = number of that atom
● In the absence of the nominal mass, the CHN data is useful to establish a ratio of the atoms (empirical formula) → CHN percentage / molar mass

Para-substituted aromatic ring

Ortho-substituted aromatic ring

Meta-substituted aromatic ring

Platinum Satellites
EXAMPLE: Vibrational spectroscopy
Vibrational modes for [Cr(Cl)4(N)]
● Point group: C4v

C4v E 2C4 C2 2σv 2σd

Unshifted atoms 6 2 2 4 2

f(R) 3 1 --1 1 1

Resultant (reducible 18 4 --2 8 4

representation)

● Irreducible representation → 4A1 + A2 + 2B1 + B2 + 5E

● Rotations → Rz ≣ A2 , Rx,y ≣ E ; Translations → z ≣ A1 , x,y ≣ E
● Remove rotation and translation from irreducible representation → ⌈vibrations = ⌈stretches + ⌈bends = 3A1 + 2B1 + B2 + E

C4v E 2C4 C2 2σv 2σd

Unshifted stretches 5 1 1 3 1

Resultant (reducible 5 2 1 6 2
representation)

● Irreducible representation (stretches) → 2A1 + B1 + E

● ⌈bends = ⌈vibrations – ⌈stretches = 3A1 + 2B1 + B2 + E – (2A1 + B1 + E) = A1 + B1
● ⌈vibrations = 3A1 + 2B1 + B2 + E ; ⌈stretches = 2A1 + B1 + E ; ⌈bends = A1 + B1
● IR active vibrations → A1 and E (the molecule is non-centrosymmetric so A1 and E are also Raman active stretches