basic theory 1. properties of nucleus spin of nucleus nuclear spin quantum number I = n/2 n : integer atomic mass number number Z A I example 1 12C, 16O, 28Si, 56Fe even even 0 odd even n : even 2H, 10B, 14N, 50V odd odd n : odd 1H, 13C, 19F, 55Mn * NMR properties of some nuclei with I = 1/2 * NMR properties of some quadrupolar nuclei (I > 1/2) number of possible spin states = 2I + 1 magnetic quantum number m = +I, +(I-1), ., -I without a magnetic field, the spin states are degenerate nucleus I No. of states m values 1 1H 1/2 2 +1/2, -1/2 11B 3/2 4 +3/2, +1/2, -1/2, -3/2 1 12C 0 1 0 14N 1 3 +1, 0, -1 1
2. nuclear Zeeman effect a nucleus with I0 in a magnetic field, 2I+1 spin states are not degenerate; they separate in energy with the largest positive m value corresponding to the lowest-energy state ex. I = 1/2 m = -1/2
Bo
DE
m = +1/2 Bo
spin state energy gh Ei = -miBo g : magnetogyric ratio 2p transition Dm = -1 for a nucleus with I = 1/2, the energy difference g h Bo DE = 2p precession some sort of uniform periodic motion, the magnetic moment wobble around the axis of applied field Lamar frequency w = gBo linear Lamar frequency u = w/2p = gBo/2p 4
Boltzmann distribution Pm=-1/2 ghBo D E/kT = e DE = Pm=+1/2 2p If Bo = 2.35 T DE = 6.63 x 10-26 J Pm= -1/2 Pm=-1/2 =0.4999959 = 0.999984 Pm= +1/2 Pm=+1/2 =0.5000041 experimental considerations sample solution solid (magic-angle spin) magnet radio-frequency transmitter spectrometer receiver decoupler recording device
magnet : permanent magnet (1 2 T) electromagnet (1.8 2.3 T) superconducting magnet (up to 13 T) two important characteristics of magnet stability sensitive to temperature homogeneity continuous wave experiment 1. frequency-sweep
2. field-sweep
information from NMR spectrum (1) chemical shift the nuclei are screen from the magnetic field Bo, the net field effective at a nucleus is Beff = Bo (1 s) s : the shielding constant each chemically distinct nucleus is associated with a characteristic frequency ex. B10H14 4 distinct B nuclei
chemical shift d relative to a standard for the isotope concerned uobs - uref 6 d = 10
spectrometer frequency
relative NMR frequency (MHz) standard nucleus (B0 = 4.7 T) reference 1H 200.0 (CH3)4Si 13C 50.2 (CH3)4Si 19F 188.2 CFCl3 29Si 39.8 (CH3)4Si 31P 81.0 85% aq. H3PO4 77Se 38.2 (CH3)2Se 119Sn 74.5 (CH3)4Sn 195Pt 43.0 [Pt(CN)6]2-
-30 20 -100 400 -200 200 -350 40 -100 250 -300 200 -1000 8000 -200 15000
(2) intensity integration of the area not for 13C (3) spin-spin coupling non-equivalent magnetically active nuclei couple each other chemically equivalent magnetically equivalent
notation
Dd >> J Dd small
A, X, M, Q A, B, C
splitting pattern 2nI + 1 coupling constant J ex. 1H, 13C NMR spectra of H13CO2-
11
0 1 2 3 4 5
1
1 1 1 1 5 3 4 2
1
1 3 6 4 5 1 1 1
12
10 10
AX2 ?? classification of the nuclei I = 1/2, 100%abundance 1H, 31P, 19F, 103Rh I = 1/2, low abundance
13C, 15N, 29Si, 77Se, 109Ag, 119Sn, 125Te, 183W, 195Pt, 199Hg
13
14
Sn(CH3)4 1H
119Sn
52 Hz
54 Hz
expanded 1H
Hz
13C
1J119 Sn-13C =
329
1J117
Sn-13C =
317
Hz
15
GeH4
Si2H6
(29Si I = , 4.7%)
16
CH3CH2SPF2
K[BH4]
17
1H
3J
PH
1H{15N}
18
[HV(CO)5]2-
J Pt-H = ?
J Pc-H = ?
19
for CH3 (or C(CH3)3) group in tertiary phosphine complexes, doublet 1H spectra indicate mutually cis arrangements and triplet spectra mutually trans
PMe2Ph
PtCl2(PMe2Ph)2
20
21
22
23
MCl3xH2O (M: Rh, Ir) (L: PR3, AsR3) (i) Ir, PEt2Ph
KH
MCl3L3 D
EtOH, 1h
MHCl2L3 (I)
MHCl2L3 (II)
158 Hz 19 Hz
18 Hz
12 Hz
24
4 Hz
9 Hz
25
206 Hz
2J 1J
HP =
9 Hz RhH = 4 Hz
2J 1J
HP =
26
(II) 13C
M-CO
M=C
27
1J
= 35 Hz 2J Pt-C = 0 Hz
Pt-C 1J
28
DEPT
29
20 lines
5 lines
[Ti(13CO)6]213C
47,49
Ti
30
(III) 31P
31
31P
31P
31P
32
31P
NMR spectra of the mixed products from the reaction of trans-[PtCl4(PEt3)2] + trans-[PtBr4(PEt3)2]
[PxFy]-
x=? y=?
33
(IV) 19F
19F
NMR spectrum of the products from the reaction: UF6 + Me3SiCl (halogen exchange)
34
(VI) 195Pt
35
2-D NMR 1. correlated spectroscopy (COSY) provide information about couplings between nuclei of a single isotopes the off-diagonal peak at a frequency (f1, f2) implies that there is a coupling between the nuclei resonating at f1 and f2 ex. COSY 11B spectrum for B10H14
B(2), B(4) (-35 ppm) B(6), B(9) (11 ppm) B(1), B(3) (13 ppm) B(5), B(7), B(8), B(10) (1 ppm)
36
2. heteronuclear correlation spectroscopy (HETCOR or HCOR) ex. HETCOR 11B/1H spectra for B10H14
37
3. nuclear Overhauser effect spectroscopy (NOSEY) identify a NOE which arises from the proximity of the two nuclei in space heteronuclear NOSEY (HOSEY) ex. 2D 1H/6Li HOSEY spectrum for tmeda adduct of 2-lithio-1-phenylpyrrole
38
ex. homonuclear 2D 13C scalar coupling (COSY) and chemical exchange (NOSEY) spectra for [Os3H2(CO)10]
ex.
O=P
39
COSY (1H1H)
COSY (1H13C)
40
exchange reactions ex. 1 31P{1H} NMR spectrum of the products derived from [Rh4(CO)9{P(OPh)3}3] under 400 atm of CO at 300 K
41
ex. 2
19F
NMR at 180 K chemical shift pattern intensity d 68 ppm doublet of triplets 2 of doublets d -61 ppm triplet of doublets 1 of narrow triplets d 68 ppm triplets of quartets 1 230 K two higher-frequency resonances broaden and lose detail 300 K coalesced to a single broad line the lowest-frequency peak remained unchanged
42
ex. 3
13C{1H}
43
ex. 4
13C{1H}
44
ex. 5
31P{1H}
45
Cl
F P SF3 Ir P CO
d 68 (2F)
-61 (1F)
46
47
48
solid state NMR spectroscopy difficulties immobility of the nuclei in solids (i) dipolar coupling are not averaged to zero ==> very broad resonance (ii) chemical shift anisotropy in solids is not averaged out ==> line broadening (iii) relaxation time T1 is very long ==> good signal-to-noise ratio is difficult to get solution: (i) magic angle sample spinning (MASS, MAS) technique an angle q = 54.7o to the magnetic field, the effect of chemically anisotropy can be averaged out (ii) cross-polarization (CP) technique overcome the problem of long relaxation time
49
ex. 2 119Sn chemical shift of Ph3SnOH in solution d 80 ppm ==> 4-coordinated, tetrahedral in solid phase d 298 ppm ==> 5-coordinated similar to Me3SnF
50
ex. 3
31P
51
52