1
RegionsRegions ofof OrganicOrganic ProtonProton ShiftsShifts
2
3
11
H NMRH NMR ChemicalChemical ShiftShift IncrementsIncrements
δδ = 0.23 += 0.23 + ΣΣ SSii ((δδ))
CCHH33ClCl δδ(calc(calc) = 2.76) = 2.76
δδ(exp(exp) = 3.1) = 3.1
CCHH22ClCl22 δδ(calc(calc) = 5.29) = 5.29
δδ(exp(exp) = 5.3) = 5.3
CCHHClCl33 δδ(calc(calc) = 7.82) = 7.82
δδ(exp(exp) = 7.27) = 7.27
Aliphatic compoundsAliphatic compounds
MethaneMethane δ(1H) = 0.23 ppm
4
11
H NMRH NMR ChemicalChemical ShiftShift IncrementsIncrements
Aromatic compoundsAromatic compounds
BenzeneBenzene δ(1H) = 7.27 ppm
δδ == 7.27 ++ ΣΣ SSii ((δδ))
X
o
m
p
5
11
H NMRH NMR ChemicalChemical ShiftShift IncrementsIncrements
δδ == 5.28 ++ ΣΣ SSii ((δδ))
OlefinicOlefinic
compoundscompounds
EthyleneEthylene
δ(1H) = 5.28 ppm
H
RGEM
RCIS
RTRANS
6
RegionsRegions ofof Inorganic ProtonInorganic Proton ShiftsShifts
OrganomOrganometaletalliclic hhyydridesdrides
Highly shieldedHighly shielded −−5 to5 to −−6060 ppmppm
[H[H--Rh(CN)Rh(CN)55]]33−−
−−10.610.6 ppmppm
H
M
M
M
M
M
M
HighlyHighly deshieldeddeshielded
[HRu[HRu66(CO)(CO)1818]]−−
16.416.4 ppmppm
[HCo[HCo66(CO)(CO)1515]]−−
23.223.2 ppmppm
7
11
H NMR ofH NMR of BoranesBoranes
1
10 5
6
8 7
2
3
4
9
HH
H
H
nidonido--Decaborane(14)Decaborane(14)
bridging Bbridging B22HH −−2.122.12 ppmppm
terminal BHterminal BH
(2,4)(2,4) 0.620.62
(5,6,8,10)(5,6,8,10) 3.133.13
(1,3)(1,3) 3.633.63
(6,9)(6,9) 3.903.90
8
11
H NMRH NMR OrganomOrganometaletalliclic HyHydridesdrides
9
RegionsRegions ofof OrganicOrganic CCarbarbonon ShiftsShifts
10
11
1313
C NMRC NMR ChemicalChemical ShiftShift IncrementsIncrements
X
ipso
o
m
p
δ(13C) = 128.5 ppm
+/- substituent X increments
for each carbon (ipso, o, m, p)
12
RegionsRegions ofof 3131
PP NMRNMR ShiftsShifts
13
RegionsRegions ofof 1919
F NMRF NMR ShiftsShifts
14
RegionsRegions ofof 7777
Se NMRSe NMR ShiftsShifts
15
RegionsRegions ofof 2929
Si NMRSi NMR ShiftsShifts
16
SilicateSilicate AAnionsnions inin AAqueousqueous AAlkalinelkaline
MMediaedia DDetectedetected byby 2929
SiSi--NMRNMR
M = OSiRM = OSiR33
D = OD = O22SiRSiR22
T = OT = O33SiRSiR
Q = OQ = O44SiSi
QQ00 = O= O44SiSi
QQ11 = O= O33SiOSiSiOSi
QQ22 = O= O22Si(Si(OSiOSi))22
QQ33 == OSiOSi((OSiOSi))33
QQ44 = Si(= Si(OSiOSi))44
17
RegionsRegions ofof 1717
O MAS NMRO MAS NMR
18
OctahedralOctahedral MetalMetal ClustersClusters
How many
derivatives and
isomers for
2 different L
??????????????
19
NMR Identification of the ClustersNMR 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 ???
20
NMR Identification of the ClustersNMR Identification of the Clusters
Series of 200 complexes
12 Signals in 31P NMR
21
NMR Identification of the ClustersNMR 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
22
NMR Identification of the ClustersNMR Identification of the Clusters
183W (I=1/2)
the satellite peaks
flanking the main P
peaks
W6S8(PR3)n(L)6-n
23
NMR Identification of the ClustersNMR Identification of the Clusters
Dean-Evans
relation
a two-parameter linear
relation
W6S8(PR3)n(L)6-n
24
NMR Identification of the ClustersNMR Identification of the Clusters
Dean-Evans relation = a two-parameter linear relation
δ(31P) = δ ref + pC + qT
δ 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)
25
NMR Identification of the ClustersNMR Identification of the Clusters
Dean-Evans relation = a two-parameter linear relation
δ(31P) = δ ref + pC + qT