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Index
NMR-basics
For small molecules having nuclei I=1/2 : Sharp lines are expected W1/2 (line width at half height) = 0-10 Hz If the nuclei has very weak interactions with the environment, Long relaxation time occur (109Ag => T1 up to 1000 s !!!) This makes the detection quite difficult!
Isotope
1H 3H 3He 13C 15N 19F 29Si 31P 57Fe 77Se 89Y 103Rh 107Ag 109Ag 111Cd
113Cd
Nat. Abundance % 99.985 0.00013 1.11 0.37 100.0 4.7 100.0 2.2 7.6 100.0 100.0 51.8 48.2 12.8 12.3
() 107 rad T-1 s-1 26.7519 28.535 -20.380 6.7283 -2.712 25.181 -5.3188 10.841 0.8661 5.12 -1.3155 -0.846 -1.087 -1.250 -5.6926 -5.9550
Frequency (MHz) 100.0 106.7 76.2 25.1 10.1 94.1 19.9 40.5 3.2 19.1 4.9 3.2 4.0 4.7 21.2 22.2
Rel. Receptivity 1.00 -5.8 * 10-7 1.8 * 10-4 3.9 * 10-6 8.3 * 10-1 3.7 * 10-4 6.6 * 10-2 7.4 * 10-7 5.3 * 10-4 1.2 * 10-4 3.2 * 10-5 3.5 * 10-5 4.9 * 10-5 1.2 * 10-3 1.3 * 10-3
Index
Spin 1/2
Isotope
117Sn
119Sn
125Te 129Xe 169Tm 171Yb 183W 187Os 195Pt 199Hg 203Tl 205Tl 207Pb
8.6
7.0 26.4 100.0 14.3 14.4 1.6 33.8 16.8 29.5 70.5 22.6
-10.021
-8.498 -7.441 -2.21 4.712 1.120 0.616 5.768 4.8154 15.436 15.589 5.540
37.3
31.5 27.8 8.3 17.6 4.2 2.3 21.4 17.9 57.1 57.6 20.9
4.5 * 10-3
2.2 * 10-3 5.7 * 10-3 5.7 * 10-4 7.8 * 10-4 1.1 * 10-5 2.0 * 10-7 3.4 * 10-3 9.8 * 10-4 5.7 * 10-2 1.4 * 10-1 2.0 * 10-3
Multinuclear NMR
There are at least four other factors we must consider Isotopic Abundance. Some nuclei such as 19F and 31P are 100% abundant (1H is 99.985%), but others such as 17O have such a low abundance (0.037%). Consider: 13C is only 1.1% abundant (need more scans than proton). Sensitivity goes with the cube of the frequency. 103Rh (100% abundant but only 0.000031 sensitivity): obtaining a spectrum for the nucleus is generally impractical. However, the nucleus can still couple to other spinactive nuclei and provide useful information. In the case of rhodium, 103Rh coupling is easily observed in the 1H and 13C spectra and the JRhX can often be used to assign structures Nuclear quadrupole. For spins greater than 1/2, the nuclear quadrupole moment is usually larger and the line widths may become excessively large. Relaxation time
These nuclei possess a quadrupole moment (deviation from spherical charge distribution) which cause extremely short relaxation time and extremely large linewidth W1/2 (up to 50 KHz)
W1/2 ~
Q = quadrupole moment qzz = electric field gradient tc = correlation time I = spin quantum number
Narrow lines can be obtained for low molecular weight (small tc) and if nuclei are embedded in ligand field of cubic (tetrahedral, octahedral) symmetry (qzz blocked)
Isotope
Spin
2H 6Li 7Li 9Be 10B 11B 14N 17O 23Na 25Mg 27Al 33S 35Cl 37Cl 39K
47Ti
49Ti 51V 55Mn
1 1 3/2 3/2 3 3/2 1 5/2 3/2 5/2 5/2 3/2 3/2 3/2 3/2 5/2 7/2 7/2 5/2
Abundance % 0.015 7.4 92.6 100.0 19.6 80.4 99.6 0.037 100.0 10.1 100.0 0.76 75.5 24.5 93.1 7.3 5.5 99.8 100.0
Freq. (MHz)
15.4 14.7 38.9 14.1 10.7 32.1 7.2 13.6 26.5 6.1 26.1 7.7 9.8 8.2 4.7 5.6 5.6 26.3 24.7
Rel. Receptivity 1.5 * 10-6 6.3 * 10-4 2.7 * 10-1 1.4 * 10-2 3.9 * 10-3 1.3 * 10-1 1.0 * 10-3 1.1 * 10-5 9.3 * 10-2 2.7 * 10-4 2.1 * 10-1 1.7 * 10-5 3.6 * 10-3 6.7 * 10-4 4.8 * 10-4 1.5 * 10-4 2.1 * 10-4 3.8 * 10-1 1.8 * 10-1
Quadrupole moment 10-28 m2 2.8 * 10-3 -8 * 10-4 -4 * 10-2 5 * 10-2 8.5 * 10-2 4.1 * 10-2 1 * 10-2 -2.6 * 10-2 1 * 10-1 2.2 * 10-1 1.5 * 10-1 -5.5 * 10-2 -1 * 10-1 -7.9 * 10-2 4.9 * 10-2 2.9 * 10-1 2.4 * 10-1 -5 * 10-2 4 * 10-1
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
Notable nuclei
spin , abundance 100%, sensitivity (H=1.0) : 0.83 2J 3 3 H-F = 45 Hz, JH-F trans = 17 Hz, JH-F Cis = 6 Hz 2J 3 F-F = 300 Hz, JF-F = - 27 Hz 29Si: spin , abundance 4.7%, sensitivity (H=1.0) : 0.0078 The inductive effect of Si typically moves 1H NMR aliphatic resonances upfield to approximately 0 to 0.5 ppm, making assignment of Si-containing groups rather easy. In addition, both carbon and proton spectra display Si satellites comprising 4.7% of the signal intensity. 31P: spin , abundance 100%, sensitivity (H=1.0) : 0.07 1J 2 H-P = 200 Hz, JH-P ~2-20 Hz, 1J 2 3 P-P = 110 Hz, JF-P ~ 1200-1400 Hz, JP-P = 1-27 Hz the chemical shift range is not as diagnostic as with other nuclei, the magnitude of the X-P coupling constants is terrific for the assignment of structures Karplus angle relationship works quite well
19F:
Notable nuclei
31P:
spin , abundance 100%, sensitivity (H=1.0) : 0.07 1J 2 H-P = 200 Hz, JH-P ~2-20 Hz, 1J 2 3 P-P = 110 Hz, JF-P ~ 1200-1400 Hz, JP-P = 1-27 Hz the chemical shift range is not as diagnostic as with other nuclei, the magnitude of the X-P coupling constants is terrific for the assignment of structures Karplus angle relationship works quite well
2J
is 153.5 Hz for the phosphine trans to the hydride, but only 19.8 Hz to the (chemically equivalent) cis phosphines.
H-P
Notable nuclei
103Rh:
spin , abundance 100%, sensitivity (H=1.0) : 0.000031 1J 1 Rh-C = 40-100 Hz, JRh-C(Cp) = 4 Hz, For example, in the 13C NMR spectrum of this linked Cp, tricarbonyl Rh dimer at 240K (the dimer undergoes fluxional bridge-terminal exchange at higher temperatures), the bridging carbonyl is observed at d232.53 and is a triplet with 1JRh-C = 46 Hz. The equivalent terminal carbonyls occur as a doublet at d190.18 with 1JRh-C = 84 Hz:
See Bitterwolf, T. E., Gambaro, A., Gottardi, F., Valle G Organometallics, 1991, 6, 1416-1420.
d - depends on electron distribution in the ground state p - depends on excited state as well. It is zero for electrons in s-orbital. This is why the proton shift is dominated by the diamagnetic term. But heavier nuclei are dominated by the paramagnetic term.
Index
Symmetry
Cl Br Si H H
H are equivalents
31
Cl Br Pt PPh3
P are non-equivalent
31
Cl
Non-equivalent nuclei could "by accident" have the same shift and this could cause confusion.
Some Non-equivalent group might also become equivalent due to some averaging process that is fast on NMR time scale. (rate of exchange is greater than the chemical shift difference)
e.g. PF5 : Fluorine are equivalent at room temperature (equatorial and axial positions are exchanging by pseudorotation)
Index
Proton - NMR
Increasing the 1 s orbital density increases the shielding
M=C MH4 MH3I 0.1 2.0 M = Si 3.2 3.4 M = Ge 3.1 3.5
MH3Br
MH3Cl (MH3)2O MH3F
2.5
2.8 3.2 4.1
4.2
4.6 4.6 4.8
4.5
5.1 5.3 5.7
Shift to low field when the metal is heavier (SnH4 - d = 3.9 ppm) Index
Index
Index
a=7.4% a=92.6%
7Li
I=1 I=3/2
: Higher resolution
: Higher sensitivity
Solvent effects are important (solvating power affects the polarity of Li-C bond and govern degree of association d covers a small range: 10 ppm Covalent compound appear at low field (2 ppm range) Coupling 1JC-Li between carbon and Lithium indicate covalent bond
Organolithium
Boron NMR
For Boron: we have the choice between 2 nuclei:
10B
a=19.6% a=80.4%
I=3 I=3/2
: Higher sensitivity
Boron NMR
Boron NMR
11B
10B
Boron can couple to other nuclei as shown here on 19F-NMR Isotopic shift
19F-NMR
11BF 4
n10B
n11B
10BF 4
JBF=0.5 Hz
JBF=1.4 Hz
C13 shifts
Saturated Carbon appear between 0-100 ppm with electronegative substituents increasing the shifts.
CH3-X : directly related to the electronegativity of X.
The effects are non-additive: CH2XY cannot be easily predicted
Shifts for aromatic compounds appear between 110-170 ppm -bonded metal alkene may be shifted up to 100 ppm: shift depends on the mode of coordination one extreme shift is CI4 d = -293 ppm !!! Metal carbonyls are found between 170-290 ppm. (very long relaxation time make their detection very difficult) Metal carbene have resonances between 250-370 ppm
Index
F-19 shifts
Wide range: 900 ppm! And are not easy to interpret. The accepted reference is now: CCl3F. With literature chemical shift, care must be taken to ensure they referenced their shifts properly. Sensitive to:
Index
F-19 shifts
The wide shift scale allow to observe all the products in the reaction of : WF6 + WCl6 --> WFnCln-6 (n=1-6)
F F W F F F F F F F W F F Cl Cl F F W F F F Cl F F W F Cl Cl
Cl F W F Cl Cl F F F
Cl Cl W Cl F F Cl
Cl F W Cl Cl F F
Cl Cl W Cl Cl Cl F
Cl Cl W Cl Cl
Index
Sn shifts
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
Sn-115 a=0.35%
H-NMR of Sn compound
2J SN119-H
= 1.046 * 2JSN117-H
2J 2J
SN119-H = SN117-H
54.3 Hz
Sn-119
3 isotopes with spin : Sn-115 a=0.35%
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
Sn-117 a=7.61%
Sn-119 a=8.58%
Sn-119 coupling
1- molecule containing 1 Sn-119 2- molecule containing Sn119, Sn117 J between Sn-119 and Sn-117 3- molecule containing two Sn119 Form an AB spectra (J=684 Hz) 4- molecule containing Sn119 and C13 J between Sn119 and C13
Dynamic NMR
p261
C13
Cycloheptatriene
Dynamic NMR
1H-NMR
P-31 Shifts
The range of shifts is 250 ppm from H3PO4 Extremes: - 460 ppm for P4 +1,362 ppm phosphinidene complexe: tBuP[Cr(CO)5]2 Interpretation of the shifts is not easy : there seems to be many contributing factors PIII covers the whole normal range: strongly substituent dependant PV narrower range: d - 50 to d + 100. Unknown can be predicted by extrapolation or interpolation PX2Y or PY3 can be predicted from those for PX3 and PXY2 The best is to compare with literature values.
Index
P-31 Shifts
Index
For example: Se(SiH3)2 and P(SiH3)3 are very close to the low frequency limit (high field) The shifts in the series SeR2 and PR3 increase in the order R= Me < Et < Pri < But There is also a remarkable correlation between 77Se and 125Te. (see picture next slide)
Index
Index
Manganese-55
Manganese-55 can be easily observed in NMR but due to its large quadrupole moment it produces broad lines 10 Hz for symmetrical environment e.g. MnO4 10,000 Hz for some carbonyl compounds. Its shift range is => 3,000 ppm As with other metals, there is a relationship between the oxidation state and chemical shielding Reference: MnVII : d = 0 ppm (MnO4-) MnI : d 1000 to 1500 Mn-I : d 1500 to -3000
55Mn
chemical shifts seems to reflect the total electron density on the metal atom
Index
Pt-195 Shifts
I= a=33.8% K2PtCl6 ref set to 0. Scale: -6000 to + 7000 ppm !!
Platinum is a heavy transition element. It has wide chemical shift scale: 13,000 ppm! The shifts depends strongly on the donor atom but vary little with long range. For example: PtCl2(PR3)2 have very similar shifts with different R Many platinum complexes have been studied by 1H, 13C and 31P NMR. But products not involving those nuclei can be missed : PtCl42Major part of Pt NMR studies deals with phosphine ligands as these can be easily studied with P-31 NMR.
Lines are broad (large CSA) large temperature dependence (1 ppm per degree)
Index
1H-NMR
CO2-
CH2=CH2
a=33.8%
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
Pt-195
H6 : dd
I = a=33.8%
JH6-Pt195 = 26 Hz
Pople Notation
H Si Cl Cl Si H F F F H H H P F I F F F
B3
A M2 X
B4
Index
When these nuclei are present in a molecule, scalar coupling must be present. Giving rise to multiplets of n+1 lines.
1J
P-H
1J
P-F
2 x 3 x 3 x 5 = 90 lines !
=> satellite signals around the major isotope. For example: WF6 as 183W has 14% abundance, the fluorine spectra should show satellite signals separated by the coupling constant between fluorine and tungsten. The central signal has 86% intensity and the satellites have 14%. This will produce 1:12:1 pattern
Index
Si-29 coupling
29Si
has 5% abundance.
H3-28Si--29Si-H3 is 10%.
Index
Platinum specie will give rise to satellite signal with a relative ratio of 1 : 4 : 1. This intensity pattern is diagnostic for the presence of platinum. If the atom is coupled to 2 Pt, the situation is more complex: 2/3 x 2/3 => no Pt spin (central resonance)
Adding the various components together we now have 1:8:18:8:1 pattern. The weak outer lines are often missed, leaving what appear to be a triplet 1:2:1 !!! Index
Index
29Si-NMR
Polymeric siloxanes are easily studied by NMR: These have terminal R3SiO Chain R2Si (O-)2 Branch R-Si(O-)3 Quaternary Si(O-)4 All these Silicon have different shifts making it possible to study the degree of polymerization and cross-linking
Index
Index
1-bound coupling
Depends on s-orbital character of the bound Hybridization of the nuclei involved 1J 3 2 CH => 125 (sp ), 160 (sp ), 250 (sp) Electronegativity is another factor: increase the coupling CCl3H => 1JCH = 209 Hz
Coupling can be used to determine coordination number of PF , PH compounds, and to distinguish axial, equatorial orientation of Fluorines. 1JPH = 180 (3 coordinate) , 1JPH = 400 (4 coordinate)
Coupling can also be used to distinguish single double bond
E.g.
P R Se R Se R R P R R
Index
2-bound coupling 2J can give structural information: There is a relationship between 2J and Bond angle => coupling range passes through zero. Therefore the sign of the coupling must be determined
P
X
P
X X
Pt2P
Pt2- P
X
Trans
Cis
Index
3-bound coupling
Depends on Dihedral angle
3J XY
= A cos 2f + B cos f + C
A, B, C : empirical constants
Index
Index
Index
Index
Index
Index
Multinuclear Approach
Proton NMR spectra: 3 groups of peaks integrating for 12:4:1 Resonances due to Methyl and CH2 have coupling with 31P And also shows satellites due to mercury coupling (199Hg 16.8%) While third resonance is broad In 31P, there is a single signal: Symmetrical compound: that has Mercury satellites In 199Hg NMR (with proton decoupling): quintet demonstrate the presence of 4 Phosphorus
Index
Heteronuclear NOE
NOE enhancement can give useful gain in signal-to-noise It is most efficient when the heteronuclei is bound to proton
NOEMAX = 1 + H/2X For nuclei having negative , NOE is negative (for 29Si, max=-1.5)
Index
At low temperature, hydrogens form an A2B2X spin system At higher temperature germanium hop from one C to the next Index
Index NMR-basics H-NMR NMR-Symmetry Heteronuclear-NMR Dynamic-NMR NMR and Organometallic compounds Special 1D-NMR