1
Regions of Organic Proton Shifts
2
3
1H NMR Chemical Shift Increments
 = 0.23 + Si ()
CH3Cl (calc) = 2.76
(exp) = 3.1
CH2Cl2 (calc) = 5.29
(exp) = 5.3
CHCl3 (calc) = 7.82
(exp) = 7.27
Aliphatic compounds
Methane (1H) = 0.23 ppm
Shoolery chemical shift rules
4
1H NMR Chemical Shift Increments
Aromatic compounds
Benzene (1H) = 7.27 ppm
 = 7.27 + Si ()
X
o
m
p
5
1H NMR Chemical Shift Increments
 = 5.28 + Si ()
Olefinic
compounds
Ethylene
(1H) = 5.28 ppm
H
RGEM
RCIS
RTRANS
6
Regions of Inorganic Proton Shifts
Organometallic hydrides
Highly shielded 5 to 60 ppm
[H-Rh(CN)5]3 10.6 ppm multiplet? unpaired electrons ?
H
M
M
M
M
M
M
Highly deshielded
[HRu6(CO)18] 16.4 ppm
[HCo6(CO)15] 23.2 ppm
7
1H NMR of Boranes
1
10 5
6
8 7
2
3
4
9
HH
H
H
nido-Decaborane(14)
bridging B2H 2.12 ppm
terminal BH
(2,4) 0.62
(5,7,8,10) 3.13
(1,3) 3.63
(6,9) 3.90
8
1H NMR Organometallic Hydrides
unpaired electrons ?
9
1H NMR of Paramagnetic
Compounds
1H NMR spectra of Fe(acac)3
CH3 CH
10
Regions of Organic Carbon Shifts
11
12
13C NMR Chemical Shift Increments
X
ipso
o
m
p
(13C) = 128.5 ppm
+/- substituent X increments
for each carbon (ipso, o, m, p)
13
Regions of 31P NMR Shifts
14
Regions of 19F NMR Shifts
15
Regions of 77Se NMR Shifts
16
Regions of 29Si NMR Shifts
SiO6
200 ppm
17
Silicate Anions in Aqueous Alkaline
Media Detected by 29Si-NMR
M = OSiR3
D = O2SiR2
T = O3SiR
Q = O4Si
Q0 = O4Si
Q1 = O3SiOSi
Q2 = O2Si(OSi)2
Q3 = OSi(OSi)3
Q4 = Si(OSi)4
18
Regions of 17O MAS NMR
H2
17O
19
Linear Correlations of the NMR Parameters with the
Number of Arene Methyls
Is diamagnetic or paramagnetic shielding affected?
B. Stibr, M. Bakardjiev, J. Holub, A. Ruzicka, Z. Padelkova, P. Stepnicka Inorg. Chem. 2011, 50, 3097–3102
B12
H12
20
Octahedral Metal Clusters
How many
derivatives and
isomers for
2 different L
??????????????
Song Jin, Jennifer Adamchuk,
Bosong Xiang, and Francis J.
DiSalvo* J. AM. CHEM. SOC.
2002, 124, 9229-9240
21
NMR Identification of the Clusters
W6S8LnL'6-n
For 2 different L, L´
there are
10 complexes
How many signals
in 31P NMR
if L´ = PR3 ???
22
NMR Identification of the Clusters
Series of 200 complexes
12 Signals in 31P NMR
23
NMR Identification of the Clusters
P-W-W-P coupling
through the cluster
core in the 31P{1H}
NMR spectra
W6S8(PR3)n(L)6-n
24
NMR Identification of the Clusters
183W (I=1/2)
the satellite peaks
flanking the main P
peaks
W6S8(PR3)n(L)6-n
25
NMR Identification of the Clusters
Dean-Evans
relation
a two-parameter linear
relation
W6S8(PR3)n(L)6-n
26
NMR Identification of the Clusters
Dean-Evans relation = a two-parameter linear relation
(31P) =  ref + pC + qT
 ref
two variables (p and q, the number of ligands L in the cis or
trans position to PR3, respectively)
two constants (C and T, characteristic of a given ligand L)
27
NMR Identification of the Clusters
Dean-Evans relation = a two-parameter linear relation
(31P) =  ref + pC + qT