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36th Organosilicon SymposiumMay 30-31, 2003
Applications of 3D-NMR In Organosilicon Chemistry
Peter L. RinaldiDepartment of ChemistryThe University of AkronAkron, Ohio 44325-3601
http://www.chemistry.uakron.edu/magnet/whatsnew.html
Outline • Introduction/Problems & Practice
– Why do 3D-NMR
– Background
– Experimental Issues
• Heteronuclear 1H/13C/29Si Triple Resonance 3D NMR– Small Molecules
– Dendrimers
– Polymers
• Heteronuclear Double Resonance 3D NMR– Applications with unlabeled materials
– Applications with isotopic labeling
Why Do 3D-NMR?
• Dispersion proportional to ν3
– Resolve resonances– Interpretation by simple inspection
• Atomic connectivity information• Simplification by filtering
– Selectively examine one part of molecule• Sensitivity 1H-detected
2D-NMR Pulse Sequence
Preparation Evolution Mixing Acquisition
t1 t2
t2
Array of Spectra Obtained with Different t1 Delays
t1
t2
FT(t2)
f2
t1
a b
t1
t1a
b
FT(t1)f2
f1
( )n1
CH2CCH3
CH3
A
B
CD E
Resonance Assignments of PIBUsing HMQC & HMBC
Tokles et al., Macromolecules, 28, 3944 (1995)
HMBCHMQC
( )tn-1tn
Preparation Acquisition
Preparation Evolution Mixing Acquisition
1D
nD
n-1
t1
Preparation Evolution Mixing Acquisition
2D
1D/2D/3D-NMR Sequences
Sample Considerations in 3D-NMR of Synthetic Polymers
• Occurrence of structural unit• Abundance of nuclei • Possibility of labeling• Molecular weight• Structural diversity• Solubility
3/15-16/97 10
1H-1
2C
1H-1
3C1H
-13C
-29
Si Min
or
Junc
tion
Bac
kbon
e01234567
Log Intensity
NMR Signal Component
MinorJunctionBackbone
Relative Signal Strength for 1H-13C-29Si Structure Fragments
HXY 3D-NMR Sequence t3
t2t1Y X
H
C
H
C
H
t1
t2τ ττ
g1g2
∆ ∆ ∆∆
X
H1
GZ
τDecouple
ϕ1
ϕ2
ϕ3
ϕ4
ϕ5t3
A C D E F G HB
Y
Saito et al. J. Magn. Resonance, 130, 135 (1998).Saito et al. J. Magn. Resonance, 132, 41 (1998).
Biological 3D-NMR Pulse Sequnces
H
N C
H
C N
H
C
H
C
O O
a H
N C
H
C N
H
C
H
C
O O
b
H
N C
H
C N
H
C
H
C
O O
c H
N C
H
C N
H
C
H
C
O O
d
H
N C
H
C N
H
C
H
C
O O
e
R1 R2
R1 R2
R1 R2
R1 R2
R1 R2
HNCO HNCA
HCACO
HCA(CO)N
15N-TOCSY-HMQC
Clore & Gronenborn, Progress NMR Spectoscopy, 23, 43 (1991).Griesinger et al., J. Magn. Resonance, 84, 14 (1989).
Biomolecular NMR Spectroscopy. J. Evans. Oxford University Press, New York, 1995.
“The devil is in the details.”
(H3CO)3Si Si(OCH3)3(H3CO)3Si
Si(OCH3)3 Si(OCH3)3Si(OCH3)3
Si(OCH3)3
Si(OCH3)3
(H3CO)3Si
Si(OCH3)3
(H3CO)3Si
Si(OCH3)3
1 3 5
2 4 6
IV
IV'
IIII'
II'
V
V'
VI
VI'
III III'
1) HSiCl3/Catalyst
2) CH3OH
CH2
Liu et al. Organometallics, 21, 3250 (2002)..
Silane Curing Agent
p pm-4 6-4 5-4 4-4 3-4 2-4 1-4 0
p pm0 .40 .81 .21 .62 .02 .4
p pm1 01 52 02 53 03 54 04 55 05 5
1H
1 3C
2 9S iI
I II II
IVV
V I
I ’
IV’
I II ’
V I’ I I’ ,V ’
a
c
b
Liu et al. Organometallics, 21, 3250 (2002).
1H/13C/29Si 1D-NMR of SilaneCuring Agent
HH
HH
HH
Si(OCH3)3(H3CO)3Si
Relative Signal Strength for Structure Components in 1H/13C/29Si Experiments
DOD = log [ IH / I HCSi fragment = 4-5
1H-1
2C
1H-1
3C
1H-1
3C-1
9F
1H-1
3C-
29Si
01234567
Log IntensityCoreSurface
HH
HH
HH
Si(OCH3)3(H3CO)3Si
3JCSi2JCSi
1JCSi1JCH = 140Hz
J = 5 HzCSi
J = 59 HzCSi
CH2CH
H
CH2 CH
CH2
CH
J = 140 HzCH
2
+5 +1A B C D E F G H
∆∆H1 ∆∆
φ1 φ5t3
φ φτ ττ τC13
2 4t2 MPF
φ3Si29
t1 MPF
Si
H
1H/13C/29Si 3D-NMR Pulse Sequence
H
HH
HH
Si(OCH3)3(H3CO)3Si
3JCSi2JCSi
1JCSi1JCH = 140Hz
Liu et al. Organometallics, 21, 3250 (2002)..
F1 (ppm)
510203040
F2(ppm)
0.60.81.01.21.41.61.82.02.22.4
F1 (ppm)
510203040
F2 (ppm)
-46-44-42-40-38
a cb1H-13C 3D Projection 1H-29Si 3D Projection1H-13C HMQC
Liu et al. Organometallics, 21, 3250 (2002)..
Projections of 1H/13C/29Si 3D-NMR HH
HH
HH
Si(OCH3)3(H3CO)3Si
3JCSi2JCSi
1JCSi1JCH = 140Hz
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F1 (ppm)
10203040
JCSi=96Hz JCSi=13Hz JCSi=5Hz b c
fd e
a
4 4
4 4
2,6 2,6
3,5
3,5
2,6 2,6
3,5
3,5
7
2
86
4
3 15
(H3CO)3Si
Si(OCH3)3
IV
IV'
26
4
315
(H3CO)3SiSi(OCH3)3
7
8II
II'
δ29Si = - 44.97
δ29Si = - 45.57
2
1
Liu et al. Organometallics, 21, 3250 (2002)..
1H/13C/29Si 3D-NMR of Silane Curing Agent
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F1 (ppm)
10203040
JCSi=96Hz JCSi=13Hz JCSi=5Hza b c
d e f
33
3 3
12 4 5 1
2 45
42 5
1
2 5
1 7
7
2
86
43 1
5
(H3CO)3Si
Si(OCH3)3
V
V'
26
43
15
(H3CO)3Si
Si(OCH3)37
8
II'
δ29Si = - 44.69
δ29Si = - 45.94
3
4
Liu et al. Organometallics, 21, 3250 (2002)..
1H/13C/29Si 3D-NMR of Silane Curing Agent
7
2
86
43
15
Si(OCH3)3
Si(OCH3)3VI'
VI
26
4
315
Si(OCH3)3Si(OCH3)3
78
IIIIII'
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F3(ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
F1 (ppm)
010203040
F1 (ppm)
10203040
JCSi=96Hz JCSi=13Hz JCSi=5Hzba
d fe
c
2
2 2
2
6
4
7
6
4
3
6 64 4
1
δ29Si = - 44.65
δ29Si = - 45.00
5
6
Liu et al. Organometallics, 21, 3250 (2002)..
1H/13C/29Si 3D-NMR of Silane Curing Agent
Relative Signal Strength for Structure Components in 1H/13C/29Si Experiments
DOD = log [ IH / I HCSi fragment = 4-5
SiCH2CH2 CH2CH2Si
Me
Si
CH2
CH2
Me
Me
Si
CH2
CH2
MeSi1H
-12C
1H-1
3C
1H-1
3C-1
9F
1H-1
3C-
29Si
01234567
Log IntensityCoreSurface
1H/29Si/13C 3D-NMR Spectrum With 1JcsiGeneration 2 Dendrimer
δ Si = 7.99ppm29
F1 (ppm)-6-226
F3(ppm)0.30.50.70.91.1
d
δ Si = 2.25ppm*29
F1 (ppm)-6-226
F3(ppm)0.30.50.70.91.1
e
F1 (ppm)-6-226
F3(ppm)0.30.50.70.91.1 δ Si = 9.95ppm29
cδ H1
δ C13
F1 (ppm)-12-6-048
F2(ppm)0.20.40.60.81.0
aδ H1
δ Si29
HMQC JHSi=5Hz
b
F2 (ppm)0246810
F3(ppm)0.20.40.60.81.0
δ H1
3D Projection
δ C13
[ 2 ]CH CH2
Me
Si ( 2CH CH iS H )2Si
Me
Me
4
H
JCH=140Hz
JCsi=59Hz
Chai et al. J. Am. Chem. Soc,121, 273 (1999).
1H/29Si/13C 3D-NMR Spectrum With 2JcsiGeneration 2 Dendrimer
[ 2 ]CH CH2
Me
Si ( 2CH CH iS H)2Si
Me
Me
4
HJCH=140Hz
JCsi=7Hz
d
δ S i = 7 . 9 9 p p m2 9
δ S i = 2 . 2 5 p p m2 9
e
δ S i = 9 . 9 5 p p m2 9
c
δ C1 3
δ H1
F 1 ( p p m )F 1 ( p p m )- 6- 226
F 3( p p m )0 . 20 . 40 . 60 . 81 . 0
F 1 ( p p m )- 6- 226
F 3( p p m )0 . 20 . 40 . 60 . 81 . 0
F 1 ( p p m )- 6- 226
F 3( p p m )0 . 20 . 40 . 60 . 81 . 0
Chai et al. J. Am. Chem. Soc,121, 273 (1999).
Dimethyl-siloxane Oligomer MD3MH
ppm0.050.150.256.00
9.015.98
6.035.98
4.654.754.851.02
a
ppm-0.5-0.00.51.01.52.02.53.03.5
b
ppm-20-15-10-505
c
Me Me
Si
Me
SiMe O Si O Si O O Si
Me
MeMe
Me
Me Me Me
H
M D1 D2 D3 MH
Chai et al., Polymer Preprints, 2001, 42(1), 15.
MD3MH 1H/13C and 1H/29Si 2D-NMRMe Me
Si
Me
SiMe O Si O Si O O Si
Me
MeMe
Me
Me Me Me
H
M D1 D2 D3 MH
F1 ( ppm )
-20-15-10-505
F2( ppm )
-0.1
-0.0
0.1
0.2
0.3
0.4
F1 ( ppm )
0.91.11.31.51.71.92.1
F2(ppm)
-0.1
-0.0
0.1
0.2
0.3
0.4
δ1H a b
δ29Siδ13C
δ1H
Chai et al., Polymer Preprints, 2001, 42(1), 15.
MD3MH 1H/13C/29Si 3D-NMR
ppm-20-18-16-14-12-10-8-6
ppm7.3
-20.13-7.14 7.06 -21.59 -22.17
0.81.42.02.6
F3(ppm)0.050.100.150.200.250.300.350.40
0.61.21.82.4
F3(ppm)0.050.100.150.200.250.300.350.40
F2 (ppm)
0.61.21.82.4
F3(ppm)0.050.100.150.200.250.300.350.40
0.61.21.82.4
F3(ppm)0.050.100.150.200.250.300.350.40
0.61.21.82.4
F3(ppm)0.050.100.150.200.250.300.350.40
*1H
*13C
*29Si
*29Si
D1 D2D3
MMH
Me Me
Si
Me
SiMe O Si O Si O O Si
Me
MeMe
Me
Me Me Me
H
M D1 D2 D3 MH
Chai et al., Polymer Preprints, 2001, 42(1), 15.
Poly(1-phenyl-1-silabutane)a
b
c
Saito, Chai, Pi, Tessier & Rinaldi, Macromolecules, 30, 1240 (1996)
1H-1
2C
1H-1
3C
1H-1
3C-1
9F
1H-1
3C-
29Si
01234567
Log IntensityChain EndBackbone
3D-NMR of PPSB
Saito et al., Macromolecules, 30, 1240 (1996)
The Power of Conditioning
Relative Signal Strength for Polymer Structure Components in 1H/13C & 1H/13C/15N Experiments
1H-1
2C
1H-1
3C
1H-1
3C-X
01234567
Log IntensityCoreSurface
DODHCN = log [ IH / I HCX fragment] = 6-7Dab-16 Dendrim er
N N
N
N
H N
H N
NH2
NH2
NH2
NH2
NH2
NH2
N
N
N
N
2
2
N H
N
N
N
N
H2N
H2N
H2N
H2N
H2N
H2N N H
N
N
2
2
DODHC = log [ IH / I HC fragment ]= 4-5
Dab-16 Dendrimer
N
N
H N NH2
NH2
NH2
N
N
2
N
DAB-16 1D-NMR Spectra
ppm1.41.82.22.6
ppm303540455055
3
65
49
8
7
10
11
1H
13C
1
2
Chai et al. Macromolecules, 33, 5395 (2000).
3D-HMQC-TOCSY Pulse Sequence
∆∆H1∆∆
φ4t3
φ2 φ3
t2 MLEV spin-lock
GARP
φ1
C13GARP
t1
A B C D E
3D-HMQC-TOCSY Slices DAB-16
p p m2 53 03 54 04 55 05 5
2.12
F3(ppm)
1.4
1.6
1.8
2.0
2.2
2.4
2.6
δH
54.15
2.12
52.32
2.12
52.19
2.12
52.13
2.12
52.06
F2 (ppm)δH 2.12
51.74
2.40
40.40
1.32
30.61
1.00
24.89
1.20
24.38
1.46
24.31δC (ppm)
Dab-16 Dendrimer
N
N
H N NH2
NH2
NH2
N
N
2
N
Chai et al. Macromolecules, 33, 5395 (2000).
C-centeredB-centered
CCCECCECE
BCC/CCBBCB(2)
ECB/BCE
BBB(3)EBB(2)
EBECBB(2)/BBC(2)
CBCEBC/CBE
EEEEEB
BEB(2)CEECEC
BEC/CEB
E-centered
E = ethylene C = carbon monoxide B = n-butylacrylate
Possible Triads of Poly(EBC)Poly(ethylene-co-butylacrylate-co-carbon monoxide)
1D 13C NMR of Labeled Poly(BCE)
200 180 160 140 120 100 80 60 40 20 ppm
Unlabeled
O
13C
OBuO
13CH
OBuO13C
1H
13CAliph
13CC=O
GZ
∆ ∆ ∆ ∆t3
t2
g1g4 g5 g6g2
ττ
Decouple
τ
t1
τ
13C
H
O OBu
C
(2)(4)
(3)
(1)(6)
(5)
(7)
t1
t3
t2
1JCH
1JCC
H2C
(1) (2) (3) (4) (5) (6) (7)
3D Pulse Sequence
Monwar et al., Polymer Preprints, 44, 257 (2003)
Decouple
g3
Truncated 3D of Poly(EB*C)
3940414243444546
F3(ppm)
2.5
2.9
2.5
2.9
174175176 40424446F1 ppm F2 ppm
HMBC HSQC
HCACO HCACO
F2(ppm)
Monwar et al., Polymer Preprints, 44, 257 (2003)
3D Slices HCACO Poly(EB*C)
ppm174175176
F3(ppm)
2.5
2.9
46.5 45.5 40.5 40.5F2 ppm
HSQC
45 40
F1=175.3 F1=174.9 F1=174.7 F1=174.2
Monwar et al., Polymer Preprints, 44, 257 (2003)
ppm173.5174.0174.5175.0175.5176.0176.5
Hardware and Environment Requirements
• Capability of most modern instruments• Stable magnetic environment• Stable room temperature• Vibration-free environment• Gradient spectroscopy• Multiple channel instrument• High sample concentrations• Computer
NMR Experiment Sizes & Times
4 hours164k x 32 x 32
80 days 16,0004k x 1k x 1k3D
4 hours164k x 1k
300 hours2,00064k x 64k2D
20 sec . 0.2564k1D
Experiment Time
File Size(Mbytes)
Data SizeDimensionality
NMR Experiment Spectral Windows (750 MHz)
1,00010-50%13C
100-1,000Only few resonance
X
16,00050-80%1H3D
20,00050%13C
2,00050-80%1H2D
10,00040,000
FullFull
1H13C
1D
Window (Hz)Window Nucleus
Data Processing
• Optimal use of folding• Optimize S:N• Linear prediction• Zero filling• Digital filtering• Live with poor digital resolution
Acknowledgments• Senior• C. Tessier• W. Youngs• L. Galya• J. Hansen• L. Wilczek• H. Yu• S. Hu
• Funding• NSF (DMR-9310642, DMR-9617477, DMR-0073346, DMR-0330816,
CHE-9412387)• Kresge Foundation• Donors to Kresge Challenge Program at University of Akron• Ohio Board of Regents, Research Challenge• University of Akron• Dupont, Dow Corning, Nalorac, Varian
StudentsT. SaitoL. WeixiaM. Chai
G. OuangC. HelferZ. PiY. Niu
StaffV. DudipalaS. StakleffT. WaglerJ. Massey G. S. HatvanyD. G. Ray
http://www.chemistry.uakron.edu/magnet/whatsnew.html
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