catalysed by lewis bases supplementary information 1 2 3 …3 kinetic plots used to determine the...
TRANSCRIPT
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1
Kinetics and mechanism of the racemic addition of trimethylsilyl cyanide to aldehydes
catalysed by Lewis bases
Supplementary Information
Michael North* Marta Omedes–Pujol and Carl Young
School of Chemistry and University Research Centre in Catalysis and Intensified Processing,
Bedson Building, University of Newcastle, Newcastle upon Tyne, UK, NE1 7RU.
Contents
Kinetic plots used to determine the overall reaction order
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1 3
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2 4
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3 5
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4 6
Kinetic plots used to determine the reaction order with respect to [PhCHO] and [Me3SiCN]
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1 7
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2 8
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3 9
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4 10
Kinetic plots used to determine the reaction order with respect to catalyst concentration
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1 11
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2 13
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3 15
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4 17
Kinetic plots used to construct the Hammett plots
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Et3N 1 19
Hammett plot for the reaction catalysed by Et3N 1 22
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NNCS 2 23
Hammett plot for the reaction catalysed by Bu4NNCS 2 26
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NN3 3 27
Hammett plot for the reaction catalysed by Bu4NN3 3 29
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NCN 4 30
Hammett plot for the reaction catalysed by Bu4NCN 4 32
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NNCS 2 in a stopped flow
kinetics system 33
Tabulated rate data for the Hammett plot in a stopped flow kinetics system 35
Hammett plot obtained using the stopped flow kinetics system 35
Kinetic plots used to construct the Eyring plots
Error analysis 36
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1 (2 mol%) 38
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2 (1 mol%) 40
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3 (0.05 mol%) 43
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4 (0.005 mol%) 46
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2
NMR stacked plots to investigate the formation of hypervalent silicon species
Addition of Et3N 1 to trimethylsilyl cyanide 49
Addition of Bu4NNCS 2 to trimethylsilyl cyanide 51
Addition of Bu4NN3 3 to trimethylsilyl cyanide 53
Addition of Bu4NCN 4 to trimethylsilyl cyanide 55
Kinetic plots used to determine the influence of water
Addition of trimethylsilyl cyanide to 3,4-dimethylbenzaldehyde catalysed by Bu4NN3 3 57
Plots showing that in the presence of water, the reaction is still first order in Et3N concentration 58
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Et3N 1 in the presence of water 60
Hammett plot for the Et3N catalysed reaction in the presence of water 62
Variable temperature kinetic study of the addition of trimethylsilyl cyanide to benzaldehyde
catalysed by Et3N in the presence of water 63
1H NMR spectra of cyanohydrin trimethylsilyl ethers
2-Trimethylsilyloxy-phenylacetonitrile 65
2-Trimethylsilyloxy-(3,5-difluorophenyl)acetonitrile 66
2-Trimethylsilyloxy-(3,4-dichlorophenyl)acetonitrile 67
2-Trimethylsilyloxy-(4-trifluoromethylphenyl)acetonitrile 68
2-Trimethylsilyloxy-(3-chlorophenyl)acetonitrile 69
2-Trimethylsilyloxy-(3-fluorophenyl)acetonitrile 70
2-Trimethylsilyloxy-(4-chlorophenyl)acetonitrile 71
2-Trimethylsilyloxy-(4-bromophenyl)acetonitrile 72
2-Trimethylsilyloxy-(4-fluorophenyl)acetonitrile 73
2-Trimethylsilyloxy-(4-thiomethylphenyl)acetonitrile 74
2-Trimethylsilyloxy-(3-methylphenyl)acetonitrile 75
2-Trimethylsilyloxy-(4-methylphenyl)acetonitrile 76
2-Trimethylsilyloxy-(3,4-dimethylphenyl)acetonitrile 77
2-Trimethylsilyloxy-(4-methoxyphenyl)acetonitrile 78
2-Trimethylsilyloxy-(4-tert-butoxyphenyl)acetonitrile 79
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Kinetic plots used to determine the overall reaction order
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1
Zero order kinetics plot First order in [PhCHO] kinetics plot
First order in [Me3SiCN] kinetics plot Second order kinetics plot
For the second order plot, the units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A =
[PhCHO], B = [Me3SiCN] and the subscripts 0 and t refer to initial concentrations and
concentrations at time t, respectively. In all cases the concentration of benzaldehyde was monitored.
y = -0.00024x + 0.45373R² = 0.94862
0
0.1
0.2
0.3
0.4
0.5
0.6
0 500 1000 1500 2000
[Ph
CH
O]
Time (s)
y = -0.00107x - 0.67016R² = 0.99843
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
y = -0.00079x - 0.58951R² = 0.99783
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[T
MS
CN
]
Time (s)
y = 0.00429x - 0.67712R² = 0.94519
-1
0
1
2
3
4
5
6
7
8
9
0 500 1000 1500 2000
un
its
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2
Zero order kinetics plot First order in [PhCHO] kinetics plot
First order in [Me3SiCN] kinetics plot Second order kinetics plot
For the second order plot, the units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A =
[PhCHO], B = [Me3SiCN] and the subscripts 0 and t refer to initial concentrations and
concentrations at time t, respectively. In all cases the concentration of benzaldehyde was monitored.
y = -0.00005x + 0.42393R² = 0.88347
0
0.1
0.2
0.3
0.4
0.5
0.6
0 1000 2000 3000 4000 5000 6000 7000 8000
[Ph
CH
O]
Time (s)
y = -0.00020x - 0.83350R² = 0.97261
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[P
hC
HO
]
Time (s)
y = -0.00016x - 0.69956R² = 0.95781
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[S
Me
3S
iCN
]
Time (s)
y = 0.00066x + 0.13184R² = 0.99897
0
1
2
3
4
5
6
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3
Zero order kinetics plot First order in [PhCHO] kinetics plot
First order in [Me3SiCN] kinetics plot Second order kinetics plot
For the second order plot, the units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A =
[PhCHO], B = [Me3SiCN] and the subscripts 0 and t refer to initial concentrations and
concentrations at time t, respectively. In all cases the concentration of benzaldehyde was monitored.
y = -0.00112x + 0.29932R² = 0.76033
-0.1
-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 50 100 150 200 250 300 350
[Ph
CH
O]
Time (s)
y = -0.00982x - 0.92436R² = 0.96776
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[P
hC
HO
]
Time (s)
y = -0.00599x - 0.84815R² = 0.90644
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[M
e3S
iCN
]
Time (s)
y = 0.05827x - 0.74457R² = 0.99580
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
units
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 3
Zero order kinetics plot First order in [PhCHO] kinetics plot
First order in [Me3SiCN] kinetics plot Second order kinetics plot
For the second order plot, the units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A =
[PhCHO], B = [Me3SiCN] and the subscripts 0 and t refer to initial concentrations and
concentrations at time t, respectively. In all cases the concentration of benzaldehyde was monitored.
y = -0.00229x + 0.40808R² = 0.87337
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0 50 100 150 200
[Ph
CH
O]
Time (s)
y = -0.01371x - 0.76338R² = 0.99796
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
y = -0.00900x - 0.69584R² = 0.97837
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[M
e3S
iCN
]
Time (s)
y = 0.07141x - 0.87612R² = 0.97674
-2
0
2
4
6
8
10
12
14
0 50 100 150 200
un
its
Time (s)
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Kinetic plots used to determine the reaction order with respect to [PhCHO] and [Me3SiCN]
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1
Kinetic plot showing that the initial rate of reaction does not depend on the initial concentration of
Me3SiCN
0
0.1
0.2
0.3
0.4
0.5
0.6
0 200 400 600 800 1000 1200 1400
[Ph
CH
O]
Time (s)
Open triangles [Me3SiCN]0 = 0.28 M, filled diamonds [Me3SiCN]0 = 0.56 M, filled squares
[Me3SiCN]0 = 1.12 M. In each case [PhCHO]0 = 0.53 M and [Et3N] = 0.01 M.
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
PhCHO
0
0.1
0.2
0.3
0.4
0.5
0.6
0 200 400 600 800 1000 1200 1400 1600 1800 2000
[Me
3Si
CN
]
Time (s)
Open triangles [PhCHO]0 = 0.25 M, filled diamonds [PhCHO]0= 0.49 M, filled squares [PhCHO]0
= 0.99 M. In each case [Me3SiCN]0 = 0.56 M and [Et3N] = 0.01 M.
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
Me3SiCN
Open triangles [Me3SiCN]0 = 0.28 M, filled diamonds [Me3SiCN]0 = 0.56 M, filled squares
[Me3SiCN]0 = 1.12 M. In each case [PhCHO]0 = 0.53 M and [Bu4NNCS] = 9.4x10-3
M.
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
PhCHO
Open triangles [PhCHO]0 = 0.27 M, filled diamonds [PhCHO]0= 0.53 M, filled squares [PhCHO]0
= 1.06 M. In each case [Me3SiCN]0 = 0.56 M and [Bu4NNCS] = 9.4x10-3 M.
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
Me3SiCN
Open triangles [Me3SiCN]0 = 0.28 M, filled diamonds [Me3SiCN]0 = 0.56 M, filled squares
[Me3SiCN]0 = 1.12 M. In each case [PhCHO]0 = 0.53 M and [Bu4NN3] = 2.3x10-3 M.
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
PhCHO
Open triangles [PhCHO]0 = 0.27 M, filled diamonds [PhCHO]0= 0.53 M, filled squares [PhCHO]0
= 1.06 M. In each case [Me3SiCN]0 = 0.56 M and [Bu4NN3] = 2.3x10-3 M.
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4
Kinetic plot showing that the initial rate of reaction does not depend on the initial concentration of
Me3SiCN
Open triangles [Me3SiCN]0 = 0.28 M, filled diamonds [Me3SiCN]0 = 0.56 M, filled squares
[Me3SiCN]0 = 1.12 M. In each case [PhCHO]0 = 0.53 M and [Bu4NCN] = 2.3x10-3 M.
Kinetic plot showing that the initial rate of reaction does depend on the initial concentration of
PhCHO
Open triangles [PhCHO]0 = 0.27 M, filled diamonds [PhCHO]0= 0.53 M, filled squares [PhCHO]0
= 1.06 M. In each case [Me3SiCN]0 = 0.56 M and [Bu4NCN] = 2.3x10-3
M.
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Kinetic plots used to determine the reaction order with respect to catalyst concentration
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1
[Et3N] = 0.001 M (corresponds to 0.2 mol%)
Run 1 Run 2
[Et3N] = 0.002 M (corresponds to 0.4 mol%)
Run 1 Run 2
y = -0.00007x - 0.72087R² = 0.98888
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 2000 4000 6000 8000 10000 12000 14000
ln[P
hC
HO
]
Time (s)
[Et3N] = 0.004 M (corresponds to 0.8 mol%)
Run 1 Run 2
y = -0.00008x - 0.70759R² = 0.98522
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 2000 4000 6000 8000 10000
ln[P
hC
HO
]
Time (s)
y = -0.00007x - 0.71254R² = 0.99348
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 2000 4000 6000 8000 10000
ln[P
hC
HO
]
Time (s)
y = -0.00013x - 0.70843 R² = 0.99500
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[P
hC
HO
]
Time (s)
y = -0.00029x - 0.65591 R² = 0.99370
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
y = -0.00039x - 0.70431 R² = 0.99218
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
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[Et3N] = 0.01 M (corresponds to 2 mol%)
Run 1 Run 2
[Et3N] = 0.02 M (corresponds to 4 mol%)
Run 1 Run 2
Plot of kobs against [1]
y = 0.7194x - 0.0937R² = 0.9929
y = 0.548x + 0.365R² = 0.9979
y = 0.8909x - 0.5523R² = 0.9863
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
0.0 5.0 10.0 15.0 20.0 25.0
ko
bsx 1
0000
[1] x 1000The dotted lines and empty data points show the rate data obtained from each of a duplicated series
of kinetic experiments. The solid line and filled data points show the average of these two data sets
and correspond to the data given in Figure 1 of the manuscript. The error in the rate constant was
estimated from the difference in slopes of the three lines in this plot.
y = -0.00058x - 0.70405 R² = 0.99726
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00072x - 0.72162 R² = 0.99260
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00113x - 0.74924 R² = 0.99561
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00177x - 0.76276 R² = 0.99590
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2
[Bu4NNCS] = 2.5x10-4
M (corresponds to 0.05 mol%)
Run 1 Run 2
[Bu4NNCS] = 5x10-4
M (corresponds to 0.1 mol%)
Run 1 Run 2
[Bu4NNCS] = 0.001 M (corresponds to 0.2 mol%)
Run 1 Run 2
y = 0.00016x - 0.01251R² = 0.99948
0
0.5
1
1.5
2
2.5
0 2000 4000 6000 8000 10000 12000 14000 16000
un
its
Time (s)
y = 0.00017x + 0.02154R² = 0.99842
0
0.5
1
1.5
2
2.5
3
0 2000 4000 6000 8000 10000 12000 14000 16000
un
its
Time (s)
y = 0.00032x + 0.17668R² = 0.99696
0
0.5
1
1.5
2
2.5
3
3.5
4
0 2000 4000 6000 8000 10000 12000
un
its
Time (s)
y = 0.00031x + 0.14371R² = 0.99699
0
0.5
1
1.5
2
2.5
3
3.5
4
0 2000 4000 6000 8000 10000 12000
un
its
Time (s)
y = 0.00066x + 0.13184R² = 0.99897
0
1
2
3
4
5
6
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.00062x + 0.16660R² = 0.99624
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
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[Bu4NNCS] = 0.002 M (corresponds to 0.4 mol%)
Run 1 Run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
Plot of kobs against [2]
y = 0.6659x - 0.1304R² = 0.9995
y = 0.6762x - 0.1391R² = 0.9999
y = 0.6557x - 0.1217R² = 0.9987
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
0.0 5.0 10.0 15.0 20.0 25.0
ko
bsx 1
0000
[2] x 10000
The dotted lines and empty data points show the rate data obtained from each of a duplicated series
of kinetic experiments. The solid line and filled data points show the average of these two data sets
and correspond to the data given in Figure 1 of the manuscript. The error in the rate constant was
estimated from the difference in slopes of the three lines in this plot.
y = 0.00134x + 0.24504R² = 0.97811
0
1
2
3
4
5
6
7
8
9
10
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.00131x + 0.24271R² = 0.99377
0
2
4
6
8
10
12
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3
[Bu4NN3] = 5x10-5
M (corresponds to 0.01 mol%)
Run 1 Run 2
[Bu4NN3] = 1x10-4
M (corresponds to 0.02 mol%)
Run 1 Run 2
[Bu4NN3] = 3x10-4
M (corresponds to 0.05 mol%)
Run 1 Run 2
y = 0.01207x - 0.04998R² = 0.99645
-0.5
0
0.5
1
1.5
2
2.5
3
3.5
4
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.01033x + 0.08923R² = 0.99594
0
0.5
1
1.5
2
2.5
3
3.5
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.02234x + 0.02083R² = 0.99193
0
1
2
3
4
5
6
7
8
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.02409x - 0.17657R² = 0.99559
-1
0
1
2
3
4
5
6
7
8
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.05827x - 0.74457R² = 0.99580
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.05612x - 0.50076R² = 0.99687
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
un
its
Time (s)
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[Bu4NN3] = 4x10-4
M (corresponds to 0.07 mol%)
Run 1 Run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
Plot of kobs against [3]
y = 1.9527x + 0.1756R² = 0.994
y = 1.9115x + 0.2382R² = 0.9985
y = 1.9939x + 0.113R² = 0.9867
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
0.0 1.0 2.0 3.0 4.0 5.0
ko
bsx 1
00
[3] x 10000
The dotted lines and empty data points show the rate data obtained from each of a duplicated series
of kinetic experiments. The solid line and filled data points show the average of these two data sets
and correspond to the data given in Figure 1 of the manuscript. The error in the rate constant was
estimated from the difference in slopes of the three lines in this plot.
y = 0.08011x - 0.16010R² = 0.99700
-5
0
5
10
15
20
25
30
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.08399x - 0.78625R² = 0.99492
-5
0
5
10
15
20
25
30
0 50 100 150 200 250 300 350
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
17
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4
[Bu4NCN] = 3x10-5
M (corresponds to 0.005 mol%)
Run 1 Run 2
[Bu4NCN] = 4x10-5
M (corresponds to 0.007 mol%)
Run 1 Run 2
[Bu4NCN] = 5x10-5
M (corresponds to 0.01 mol%)
Run 1 Run 2
y = -0.00141x - 0.70495 R² = 0.99517
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 50 100 150 200 250 300 350
ln[P
hC
HO
]
Time (s)
y = -0.00123x - 0.72412 R² = 0.99770
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00174x - 0.75536R² = 0.99605
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00139x - 0.72048R² = 0.99519
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00313x - 0.70129R² = 0.99267
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
y = -0.00251x - 0.76872R² = 0.99456
-2.5
-2
-1.5
-1
-0.5
0
0 100 200 300 400 500 600 700
ln[P
hC
HO
]
Time (s)
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18
[Bu4NCN] = 2x10-4
M (corresponds to 0.03 mol%)
Run 1 Run 2
[Bu4NCN] = 3x10
-4 M (corresponds to 0.05 mol%)
Run 1 Run 2
Plot of kobs against [4]
y = 0.4411x + 0.0109R² = 0.9894
y = 0.4302x + 0.2058R² = 0.9819
y = 0.4519x - 0.1839R² = 0.9946
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
0.0 5.0 10.0 15.0 20.0 25.0 30.0
ko
bsx 1
000
[4] x 100000The dotted lines and empty data points show the rate data obtained from each of a duplicated series
of kinetic experiments. The solid line and filled data points show the average of these two data sets
and correspond to the data given in Figure 1 of the manuscript. The error in the rate constant was
estimated from the difference in slopes of the three lines in this plot.
y = -0.00783x - 0.73800R² = 0.99411
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
y = -0.00829x - 0.66285R² = 0.99453
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
y = -0.01371x - 0.76338R² = 0.99796
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
y = -0.01374x - 0.64160R² = 0.99522
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
19
Kinetic plots used to construct the Hammett plots
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Et3N 1
Benzaldehyde run 1 Benzaldehyde run 2
3-Chlorobenzaldehyde run 1 3-Chlorobenzaldehyde run 2
3-Fluorobenzaldehyde run 1 3-Fluorobenzaldehyde run 2
y = -0.00058x - 0.70405 R² = 0.99726
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00072x - 0.72162 R² = 0.99260
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00131x - 0.70284 R² = 0.99768
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00146x - 0.69454 R² = 0.99427
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
y = -0.00114x - 0.70140 R² = 0.99576
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
y = -0.00130x - 0.72761 R² = 0.99926
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
20
4-Chlorobenzaldehyde run 1 4-Chlorobenzaldehyde run 2
4-Fluorobenzaldehyde run 1 4-Fluorobenzaldehyde run 2
4-Thiomethylbenzaldehyde run 1 4-Thiomethylbenzaldehyde run 2
3-Methylbenzaldehyde run 1 3-Methylbenzaldehyde run 2
y = -0.00068x - 0.71570 R² = 0.99811
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[P
hC
HO
]
Time (s)
y = -0.00075x - 0.68861 R² = 0.99762
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[P
hC
HO
]
Time (s)
y = -0.00105x - 0.71859 R² = 0.99500
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
y = -0.00090x - 0.69143 R² = 0.99824
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00085x - 0.69767 R² = 0.99503
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00070x - 0.73564 R² = 0.99767
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00049x - 0.67083 R² = 0.99716
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
y = -0.00063x - 0.67750 R² = 0.99729
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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21
4-Methylbenzaldehyde run 1 4-Methylbenzaldehyde run 2
3,4-Dimethylbenzaldehyde run 1 3,4-Dimethylbenzaldehyde run 2
4-Methoxybenzaldehyde run 1 4-Methoxybenzaldehyde run 2
y = -0.00098x - 0.72362 R² = 0.99806
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00085x - 0.67174 R² = 0.99708
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00043x - 0.67114 R² = 0.99876
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
y = -0.00041x - 0.68288 R² = 0.99723
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[P
hC
HO
]
Time (s)
y = -0.00050x - 0.76163 R² = 0.99866
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[P
hC
HO
]
Time (s)
y = -0.00059x - 0.71440 R² = 0.99743
-6
-5
-4
-3
-2
-1
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
22
Hammett plot for the reaction catalysed by Et3N 1
y = 0.6136xR² = 0.5067
-0.2
-0.1
0
0.1
0.2
0.3
0.4
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
log
.k(A
rCH
O)/ lo
g.k
(Ph
CH
O)
s
4-OMe
4-Me
3-Me
H
4-F
4-SMe
4-Cl
3-Cl
3-F
3,4-diMe
Only the average of two individual rate constants were used to construct this graph.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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23
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NNCS 2
Benzaldehyde run 1 Benzaldehyde run 2
3,5-Difluororobenzaldehyde run 1 3,5-Difluororobenzaldehyde run 2
4-Trifluoromethylbenzaldehyde run 1 4-Trifluoromethylbenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.00066x + 0.13184R² = 0.99897
0
1
2
3
4
5
6
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.00062x + 0.16660R² = 0.99624
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.24351x - 0.08625R² = 0.99360
0
5
10
15
20
25
0 20 40 60 80 100
un
its
Time (s)
y = 0.32957x + 0.27041R² = 0.99620
0
5
10
15
20
25
30
0 10 20 30 40 50 60 70 80
un
its
Time (s)
y = 0.09012x + 0.11058R² = 0.99890
0
5
10
15
20
25
30
35
0 50 100 150 200 250 300 350 400
un
its
Time (s)
y = 0.10486x - 0.58462R² = 0.99704
0
5
10
15
20
25
30
35
40
0 50 100 150 200 250 300 350 400
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
24
3-Chlorobenzaldehyde run 1 3-Chlorobenzaldehyde run 2
3-Fluorobenzaldehyde run 1 3-Fluorobenzaldehyde run 2
4-Chlorobenzaldehyde run 1 4-Chlorobenzaldehyde run 2
4-Fluorobenzaldehyde run 1 4-Fluorobenzaldehyde run 2
y = 0.03762x - 0.00148R² = 0.99795
0
5
10
15
20
25
0 100 200 300 400 500 600 700
un
its
Time (s)
y = 0.03308x - 0.03596R² = 0.99339
0
5
10
15
20
25
0 100 200 300 400 500 600 700
un
its
Time (s)
y = 0.00293x + 0.01754R² = 0.99800
0
1
2
3
4
5
6
0 500 1000 1500 2000 2500
un
its
Time (s)
y = 0.00304x - 0.02836R² = 0.99459
0
1
2
3
4
5
6
0 500 1000 1500 2000
un
its
Time (s)
y = 0.00850x + 0.11473R² = 0.99932
0
2
4
6
8
10
12
14
16
18
0 500 1000 1500 2000
un
its
Time (s)
y = 0.00819x + 0.28455R² = 0.99845
0
2
4
6
8
10
12
14
16
0 500 1000 1500 2000
un
its
Time (s)
y = 0.00047x + 0.02452R² = 0.99147
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0.00056x - 0.01016R² = 0.99821
0
0.5
1
1.5
2
2.5
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
25
4-Thiomethylbenzaldehyde run 1 4-Thiomethylbenzaldehyde run 2
3-Methylbenzaldehyde run 1 3-Methylbenzaldehyde run-2
4-Methylbenzaldehyde run 1 4-Methylbenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.00078x - 0.00702R² = 0.99954
0
0.5
1
1.5
2
2.5
3
3.5
4
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
y = 0.00076x + 0.02525R² = 0.99597
0
0.5
1
1.5
2
2.5
3
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0.00034x + 0.00437R² = 0.99723
0
0.5
1
1.5
2
2.5
3
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.00034x + 0.00205R² = 0.99559
0
0.5
1
1.5
2
2.5
3
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0.00064x - 0.02137R² = 0.99521
0
0.5
1
1.5
2
2.5
3
3.5
4
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
y = 0.00068x - 0.06338R² = 0.99581
0
0.5
1
1.5
2
2.5
3
3.5
4
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
26
3,4-Dimethylbenzaldehyde run 1 3,4-Dimethylbenzaldehyde run 2
4-Methoxybenzaldehyde run 1 4-Methoxybenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
Hammett plot for the reaction catalysed by Bu4NNCS 2
y = 3.58x + 0.10R² = 0.93
y = 3.55x + 0.08R² = 0.92
y = 3.61x + 0.12R² = 0.93
-1
-0.5
0
0.5
1
1.5
2
2.5
3
-0.3 -0.1 0.1 0.3 0.5 0.7
log
.k(A
rCH
O)/ lo
g.k
(Ph
CH
O)
s
4-OMe
4-Me
3-Me
H
4-F
4-SMe
4-Cl
3-Cl
3-F
3,4-diMe
3,5-diF
4-CF3
The filled diamonds and solid line correspond to the average rate data for each aldehyde whilst the
unfilled squares and triangles and the broken lines correspond to each individual set of rate data.
y = 0.00009x + 0.00677R² = 0.99924
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
0 5000 10000 15000 20000
un
its
Time (s)
y = 0.00010x - 0.07167R² = 0.98210
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 5000 10000 15000 20000
un
its
Time (s)
y = 0.00014x + 0.02530R² = 0.99381
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 2000 4000 6000 8000 10000
un
its
Time (s)
y = 0.00014x + 0.01893R² = 0.99247
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 2000 4000 6000 8000 10000
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
27
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NN3 3
Benzaldehyde run 1 Benzaldehyde run 2
4-Chlorobenzaldehyde run 1 4-Chlorobenzaldehyde run 2
4-Fluorobenzaldehyde run 1 4-Fluorobenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.05827x - 0.74457R² = 0.99580
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.05612x - 0.50076R² = 0.99687
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
un
its
Time (s)
y = 0.21151x - 0.63946R² = 0.99055
-5
0
5
10
15
20
0 20 40 60 80 100
un
its
Time (s)
y = 0.19690x + 0.19410R² = 0.99089
0
2
4
6
8
10
12
14
16
18
20
0 20 40 60 80 100
un
its
Time (s)
y = 0.06594x - 0.27429R² = 0.99230
-2
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.05064x + 0.68660R² = 0.98682
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
28
4-Thiomethylbenzaldehyde run 1 4-Thiomethylbenzaldehyde run 2
3-Methylbenzaldehyde run 1 3-Methylbenzaldehyde run 2
4-Methylbenzaldehyde run 1 4-Methylbenzaldehyde run 2
3,4-Dimethylbenzaldehyde run 1 3,4-Dimethylbenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.06255x + 0.13894R² = 0.99713
0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.07767x + 0.24085R² = 0.99696
0
5
10
15
20
25
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.02713x - 0.15681R² = 0.99608
-2
0
2
4
6
8
10
12
0 50 100 150 200 250 300 350 400
un
its
Time (s)
y = 0.03119x - 0.30922R² = 0.99213
-2
0
2
4
6
8
10
12
14
0 50 100 150 200 250 300 350 400
un
its
Time (s)
y = 0.03280x - 0.15722R² = 0.99553
-2
0
2
4
6
8
10
12
14
16
0 100 200 300 400 500
un
its
Time (s)
y = 0.02813x - 0.50489R² = 0.98968
-2
0
2
4
6
8
10
12
14
16
18
0 100 200 300 400 500 600 700
un
its
Time (s)
y = 0.00553x + 0.07410R² = 0.99933
0
2
4
6
8
10
12
14
16
0 500 1000 1500 2000 2500 3000
un
its
Time (s)
y = 0.00473x + 0.03180R² = 0.99627
0
2
4
6
8
10
12
14
0 500 1000 1500 2000 2500 3000
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
29
4-Methoxybenzaldehyde run 1 4-Methoxybenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
Hammett plot for the reaction catalysed by Bu4NN3 3
y = 2.98x - 0.07
R² = 0.91
y = 2.98x - 0.07
R² = 0.92
y = 2.97x - 0.07
R² = 0.89
-1.1
-0.9
-0.7
-0.5
-0.3
-0.1
0.1
0.3
0.5
0.7
-0.3 -0.2 -0.1 0 0.1 0.2 0.3
log
.k(A
rCH
O)/
log
.k(P
hC
HO
)
s
4-OMe
4-Me3-Me
H 4-F4-SMe
3,4-diMe
4-Cl
The filled diamonds and solid line correspond to the average rate data for each aldehyde whilst the
unfilled squares and triangles and the broken lines correspond to each individual set of rate data.
y = 0.00870x - 0.30771R² = 0.99734
-5
0
5
10
15
20
25
30
35
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0.00894x + 0.18519R² = 0.99490
0
2
4
6
8
10
12
14
16
18
0 500 1000 1500 2000
un
its
Time (s)
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30
Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NCN 4
Benzaldehyde run 1 Benzaldehyde run 2
3-Chlorobenzaldehyde run 1 3-Chlorobenzaldehyde run 2
3-Fluorobenzaldehyde run 1 3-Fluorobenzaldehyde run 2
4-Chlorobenzaldehyde run 1 4-Chlorobenzaldehyde run 2
y = -0.00141x - 0.70495R² = 0.99517
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 50 100 150 200 250 300 350
ln[P
hC
HO
]
Time (s)
y = -0.00123x - 0.72412R² = 0.99770
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.03169x - 0.71783 R² = 0.98803
-3
-2.5
-2
-1.5
-1
-0.5
0
0 10 20 30 40 50 60 70
ln[A
rCH
O]
Time (s)
y = -0.03302x - 0.64298 R² = 0.99315
-3
-2.5
-2
-1.5
-1
-0.5
0
0 10 20 30 40 50 60 70
ln[A
rCH
O]
Time (s)
y = -0.01081x - 0.75194 R² = 0.98880
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[A
rCH
O]
Time (s)
y = -0.01176x - 0.72450 R² = 0.99697
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[A
rCH
O]
Time (s)
y = -0.00876x - 0.60056 R² = 0.99331
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[A
rCH
O]
Time (s)
y = -0.00991x - 0.56250 R² = 0.99363
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 50 100 150 200 250 300 350
ln[A
rCH
O]
Time (s)
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31
4-Fluorobenzaldehyde run 1 4-Fluorobenzaldehyde run 2
4-Thiomethylbenzaldehyde run 1 4-Thiomethylbenzaldehyde run 2
3-Methylbenzaldehyde run 1 3-Methylbenzaldehyde run 2
4-Methylbenzaldehyde run 1 4-Methylbenzaldehyde run 2
y = -0.00167x - 0.70495 R² = 0.99796
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[A
rCH
O]
Time (s)
y = -0.00193x - 0.66416 R² = 0.99549
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[A
rCH
O]
Time (s)
y = -0.00092x - 0.74457 R² = 0.99097
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[A
rCH
O]
Time (s)
y = -0.00102x - 0.68662 R² = 0.99788
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[A
rCH
O]
Time (s)
y = -0.00042x - 0.62938 R² = 0.99460
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[A
rCH
O]
Time (s)
y = -0.00038x - 0.72482 R² = 0.99257
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[A
rCH
O]
Time (s)
y = -0.00033x - 0.69561 R² = 0.99381
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[A
rCH
O]
Time (s)
y = -0.00032x - 0.67346 R² = 0.99598
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[A
rCH
O]
Time (s)
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32
3,4-Dimethylbenzaldehyde run 1 3,4-Dimethylbenzaldehyde run 2
4-Methoxybenzaldehyde run 1 4-Methoxybenzaldehyde run 2
Hammett plot for the reaction catalysed by Bu4NCN
y = 3.50x - 0.07R² = 0.97
y = 3.50x - 0.11R² = 0.97
y = 3.51x - 0.03R² = 0.97
-1.5
-1
-0.5
0
0.5
1
1.5
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
log
.k(A
rCH
O)/ lo
g.k
(Ph
CH
O)
s
4-OMe
4-Me3-Me
H
4-F
4-SMe
4-Cl
3-Cl
3-F
3,4-diMe
The filled diamonds and solid line correspond to the average rate data for each aldehyde whilst the
unfilled squares and triangles and the broken lines correspond to each individual set of rate data.
y = -0.00023x - 0.67205 R² = 0.99546
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[A
rCH
O]
Time (s)
y = -0.00025x - 0.65436 R² = 0.99572
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[A
rCH
O]
Time (s)
y = -0.00012x - 0.75648 R² = 0.98712
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[A
rCH
O]
Time (s)
y = -0.00014x - 0.66922 R² = 0.99495
-3
-2.5
-2
-1.5
-1
-0.5
0
0 2000 4000 6000 8000 10000 12000 14000 16000
ln[A
rCH
O]
Time (s)
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Addition of trimethylsilyl cyanide to benzaldehydes catalysed by Bu4NNCS 2 in a stopped
flow kinetics system
Benzaldehyde run 1 Benzaldehyde run 2
3,5-Difluororobenzaldehyde run 1 3,5-Difluororobenzaldehyde run 2
3-Chlorobenzaldehyde run 1 3-Chlorobenzaldehyde run 2
3-Fluorobenzaldehyde run 1 3-Fluorobenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.00055x + 0.01753R² = 0.99980
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 200 400 600 800 1000 1200 1400
un
its
Time (s)
y = 0.00055x + 0.01732R² = 0.99981
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 200 400 600 800 1000 1200 1400
un
its
Time (s)
y = 0.03853x + 0.01430R² = 0.99945
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 20 40 60 80 100 120 140
un
its
Time (s)
y = 0.03918x + 0.00543R² = 0.99958
-1
0
1
2
3
4
5
0 20 40 60 80 100 120 140
un
its
Time (s)
y = 0.00543x - 0.01360R² = 0.99968
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.00552x - 0.01534R² = 0.99973
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.00781x - 0.04946R² = 0.99927
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 50 100 150 200 250 300
un
its
Time (s)
y = 0.00777x - 0.04857R² = 0.99929
-0.1
0.4
0.9
1.4
1.9
2.4
0 50 100 150 200 250 300
un
its
Time (s)
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4-Chlorobenzaldehyde run 1 4-Chlorobenzaldehyde run 2
4-Fluorobenzaldehyde run 1 4-Fluorobenzaldehyde run 2
4-Thiomethylbenzaldehyde run 1 4-Thiomethylbenzaldehyde run 2
3-Methylbenzaldehyde run 1 3-Methylbenzaldehyde run 2
The units for the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B =
[Me3SiCN] and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively. The concentration of benzaldehyde was monitored.
y = 0.00637x - 2.18926R² = 0.99938
0
1
2
3
4
5
6
7
8
9
10
900 1100 1300 1500 1700 1900
un
its
Time (s)
y = 0.00765x - 3.20053R² = 0.99797
-0.1
1.9
3.9
5.9
7.9
9.9
11.9
900 1100 1300 1500 1700 1900
un
its
Time (s)
y = 0.00068x + 0.04309R² = 0.99915
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 200 400 600 800 1000
un
its
Time (s)
y = 0.00068x + 0.04315R² = 0.99917
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 200 400 600 800 1000
un
its
Time (s)
y = 0.00043x + 1.00964R² = 0.99554
0
0.2
0.4
0.6
0.8
1
1.2
1.4
300 350 400 450 500 550 600 650
un
its
Time (s)
y = 0.00043x + 1.01212R² = 0.99555
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.5
300 350 400 450 500 550 600 650
un
its
Time (s)
y = 0.00080x + 0.17907R² = 0.99879
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
600 800 1000 1200 1400 1600
un
its
Time (s)
y = 0.00083x + 0.17632R² = 0.99878
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.5
600 800 1000 1200 1400 1600
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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35
Tabulated rate data for the Hammett plot in a stopped flow kinetics system
aldehyde s k (M-1
s-1
)a
3,5-F2C6H3CHO 0.68 0.0388 ± 0.0003
3-ClC6H4CHO 0.37 0.00543 ± 0.00001
3-FC6H4CHO 0.34 0.00779 ± 0.00002
4-ClC6H4CHO 0.23 0.0070 ± 0.0006
4-FC6H4CHO 0.06 0.00068 ± 0.00001
PhCHO 0 0.00055 ± 0.00001
4-MeSC6H4CHO 0 0.00043 ± 0.00001
3-MeC6H4CHO -0.06 0.00082 ± 0.00001
a Average of two experiments
Hammett plot obtained using the stopped flow kinetics system
y = 2.69x + 0.11R² = 0.91 y = 2.68x + 0.11
R² = 0.92
y = 2.69x + 0.12R² = 0.90
-0.5
0
0.5
1
1.5
2
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
log
.k(A
rCH
O)/ lo
g.k
(Ph
CH
O)
s
3-Me
H 4-F
4-SMe
4-Cl 3-Cl
3-F
3,5-diF
The filled diamonds and solid line correspond to the average rate data for each aldehyde whilst the
unfilled squares and triangles and the broken lines correspond to each individual set of rate data.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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36
Kinetic plots used to construct the Eyring plots
Error analysis
To provide errors in the enthalpy and entropy of activation, the following approach was adopted.
1. Two solution of benzaldehyde in dichloromethane were prepared, one corresponding to the
concentration of benzaldehyde at the start of the kinetics experiments and the other to 80%
conversion (i.e. a concentration 20% of the first solution). Ten samples were removed from
each of these solutions using the same microlitre syringe used for the kinetics study and each
sample was analysed at the same wavelength, using the same UV spectrophotometer used for
the kinetics work. The resulting data is presented graphically below and allowed the error in
the measurement of the concentrations at the start and end of the kinetics experiments to be
determined. On the basis of these data, an error of +/- 5% was assumed in all data points in all
variable temperature kinetics plots.
Benzaldehyde concentration corresponding to 0% conversion
1.76
1.78
1.8
1.82
1.84
1.86
1.88
0 2 4 6 8 10
Ab
so
rbance
Sample number
All of the data points lie within +/- 3.1% of the mean value of 1.817
Benzaldehyde concentration corresponding to 80% conversion
0.26
0.265
0.27
0.275
0.28
0.285
0.29
0.295
0 2 4 6 8 10
Ab
so
rbance
Sample number
All of the data points lie within +/- 4.6% of the mean value of 0.2772
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37
2. For each variable temperature kinetics plot, in addition to determining the best fit line through
the data, the lines corresponding to an error of +/- 5% in the absorbance reading used to
calculate the first and last data point were determined (these are shown on all the graphs in the
following pages). These lines gave an indication of the error in the best fit line gradient.
3. Each variable temperature kinetics plot was conducted in duplicate, and the average of the
two gradients was used to determine the data point for the Eyring plot. However, the error
bars for this data point were determined from the maximum and minumim gradients of either
individual kinetics plot.
4. The maximum and minimum slope passing through the highest and lowest temperature points
were used to determine the errors in the gradient and intercept of the Eyring plot and hence
the error limits in the enthalpy and entropy of activation.
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38
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Et3N 1 (2 mol%)
Reaction at +10 oC run 1 Reaction at +10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Reaction at 0 oC run 1 Reaction at 0
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Reaction at -10 oC run 1 Reaction at -10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
y = -0.00243x - 0.67352 R² = 0.99708
y = -0.00254x - 0.65714
y = -0.00232x - 0.75722
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000
ln[P
hC
HO
]
Time (s)
y = -0.00246x - 0.71001 R² = 0.99787
y = -0.00252x - 0.65714
y = -0.00230x - 0.75722
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000
ln[P
hC
HO
]
Time (s)
y = -0.00058x - 0.70405 R² = 0.99726
y = -0.00066x - 0.65714
y = -0.00049x - 0.75722
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00072x - 0.72162 R² = 0.99260
y = -0.00083x - 0.65714
y = -0.00066x - 0.75722
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200 1400
ln[P
hC
HO
]
Time (s)
y = -0.00040x - 0.72228 R² = 0.99566
y = -0.00047x - 0.65714
y = -0.00035x - 0.75722
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
y = -0.00031x - 0.70906 R² = 0.99470
y = -0.00035x - 0.65714
y = -0.00024x - 0.75722
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
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39
Reaction at -20 oC run 1 Reaction at -20
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Eyring plot
The filled triangles correspond to the average of the two individual rate measurements at each
temperature and the solid line (and equation with R2 value) is the best fit line through these data
points. This corresponds to the data given in Figure 4 of the manuscript. The horizontal lines above
and below each diamond correspond to the maximum and minimum value for that data point from
either of the individual rate measurements. The broken lines (and equations without R2 values)
correspond to the limiting values for the best fit line based on the error limits for the highest and
lowest temperature points. The data in Table 5 of the manuscript were obtained by averaging the
maximum and minimum values of Hǂ and S
ǂ obtained from the broken lines rather than from the
solid line so as to ensure that the quoted values were at the midpoint of the maximum and minimum
values.
y = -0.00014x - 0.74070 R² = 0.98054
y = -0.00018x - 0.65714
y = -0.00012x - 0.75722
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 500 1000 1500 2000 2500 3000 3500 4000
ln[P
hC
HO
]
Time (s)
y = -0.00016x - 0.69764 R² = 0.99742
y = -0.00017x - 0.65714
y = -0.00014x - 0.75722
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1000 2000 3000 4000 5000 6000 7000 8000
ln[P
hC
HO
]
Time (s)
y = -6.1315x + 9.8035 R² = 0.9644 y = -7.0009x + 13.092
y = -5.7992x + 8.7508
-15.0
-14.5
-14.0
-13.5
-13.0
-12.5
-12.0
-11.5
-11.0
3.5 3.6 3.7 3.8 3.9 4.0
ln(k
1obs/T
)
1000/T (K)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
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40
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NNCS 2 (1 mol%)
Reaction at +20 oC run 1 Reaction at +20
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively.
Reaction at +10 oC run 1 Reaction at +10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively.
y = 0.00805x - 0.05064 R² = 0.99804
y = 0.00901x - 0.74070
y = 0.00732x + 0.77870
-2
3
8
13
18
0 500 1000 1500 2000
units
Time (s)
y = 0.00780x + 0.36660 R² = 0.98376
y = 0.00847x - 0.74070
y = 0.00678x + 0.77870
-2
0
2
4
6
8
10
12
14
16
0 500 1000 1500 2000
units
Time (s)
y = 0.00512x - 0.55130 R² = 0.98736
y = 0.00571x - 0.74070
y = 0.00486x + 0.77870
-2
3
8
13
18
23
0 500 1000 1500 2000 2500 3000 3500 4000
units
Time (s)
y = 0.00493x - 0.55193 R² = 0.99648
y = 0.00520x - 0.74070
y = 0.00436x + 0.77870
-2
0
2
4
6
8
10
12
14
16
18
0 500 1000 1500 2000 2500 3000 3500 4000
units
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
41
Reaction at 0 oC run 1 Reaction at 0
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively.
Reaction at -10 oC run 1 Reaction at -10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively.
y = 0.00281x - 0.06677 R² = 0.99884
y = 0.00322x - 0.74070
y = 0.00237x + 0.77870
-2
0
2
4
6
8
10
12
0 500 1000 1500 2000 2500 3000 3500 4000
units
Time (s)
y = 0.00291x - 0.05041 R² = 0.99348
y = 0.00374x - 0.74070
y = 0.00206x + 0.77870
-2
-1
0
1
2
3
4
5
6
7
0 500 1000 1500 2000
units
Time (s)
y = 0.00148x - 0.15042 R² = 0.99848
y = 0.00167x - 0.74070
y = 0.00125x + 0.77870
-2
0
2
4
6
8
10
12
0 1000 2000 3000 4000 5000 6000 7000 8000
units
Time (s)
y = 0.00159x - 0.23519 R² = 0.99333
y = 0.00178x - 0.74070
y = 0.00136x + 0.77870
-2
0
2
4
6
8
10
12
14
0 1000 2000 3000 4000 5000 6000 7000 8000
units
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
42
Eyring plot
y = -3.9576x + 3.0155R² = 0.9984
y = -4.7876x + 5.9362
y = -3.1522x + 0.0749
-12.5
-12.0
-11.5
-11.0
-10.5
-10.0
3.3 3.4 3.5 3.6 3.7 3.8 3.9
ln(k
2o
bs/T
)
1000/T (K)
The filled triangles correspond to the average of the two individual rate measurements at each
temperature and the solid line (and equation with R2 value) is the best fit line through these data
points. This corresponds to the data given in Figure 4 of the manuscript. The horizontal lines above
and below each diamond correspond to the maximum and minimum value for that data point from
either of the individual rate measurements. The broken lines (and equations without R2 values)
correspond to the limiting values for the best fit line based on the error limits for the highest and
lowest temperature points. The data in Table 5 of the manuscript were obtained by averaging the
maximum and minimum values of Hǂ and S
ǂ obtained from the broken lines rather than from the
solid line so as to ensure that the quoted values were at the midpoint of the maximum and minimum
values.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
43
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NN3 3 (0.05 mol%)
Reaction at +10 oC run 1 Reaction at +10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively. The
concentration of benzaldehyde was monitored.
Reaction at 0 oC run 1 Reaction at 0
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively. The
concentration of benzaldehyde was monitored.
y = 0.10852x - 0.21463 R² = 0.99384
y = 0.11825x - 0.74070
y = 0.10595x + 0.77870
-2
3
8
13
18
23
28
0 50 100 150 200 250
units
Time (s)
y = 0.10641x - 0.37451 R² = 0.99258
y = 0.11130x - 0.74070
y = 0.09915x + 0.77870
-2
3
8
13
18
23
28
0 50 100 150 200 250
units
Time (s)
y = 0.05827x - 0.74457 R² = 0.99580
y = 0.06070x - 0.74070
y = 0.05043x + 0.77870
-2
0
2
4
6
8
10
12
14
16
18
20
0 50 100 150 200 250 300
units
Time (s)
y = 0.05612x - 0.50076 R² = 0.99687
y = 0.05930x - 0.74070
y = 0.04927x + 0.77870
-2
0
2
4
6
8
10
12
14
16
18
20
0 50 100 150 200 250 300 350
units
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
44
Reaction at -10 oC run 1 Reaction at -10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively. The
concentration of benzaldehyde was monitored.
Reaction at -20 oC run 1 Reaction at -20
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points. The units for
the vertical scale are: ln[(B0At)/(BtA0)]/(A0B0) where: A = [PhCHO], B = [Me3SiCN] and the
subscripts 0 and t refer to initial concentrations and concentrations at time t, respectively. The
concentration of benzaldehyde was monitored.
y = 0.02868x - 0.20676 R² = 0.99768
y = 0.03337x - 0.74070
y = 0.02340x + 0.77870
-2
0
2
4
6
8
10
12
0 50 100 150 200 250 300 350
units
Time (s)
y = 0.02803x - 0.29383 R² = 0.99118
y = 0.03370x - 0.74070
y = 0.02357x + 0.77870
-2
0
2
4
6
8
10
12
0 50 100 150 200 250 300 350
units
Time (s)
y = 0.01438x + 0.02979 R² = 0.99831
y = 0.01693x - 0.74070
y = 0.01186x + 0.77870
-2
0
2
4
6
8
10
12
0 100 200 300 400 500 600 700
units
Time (s)
y = 0.01432x - 0.10668 R² = 0.99847
y = 0.01685x - 0.74070
y = 0.01179x + 0.77870
-2
0
2
4
6
8
10
12
0 100 200 300 400 500 600 700
un
its
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
45
Eyring plot
y = -4.5584x + 8.2238R² = 0.9995
y = -5.2226x + 10.655
y = -3.9416x + 5.9574
-10.5
-10.0
-9.5
-9.0
-8.5
-8.0
-7.5
3.5 3.6 3.7 3.8 3.9 4.0
ln(k
2o
bs/T
)
1000/T (K)
The filled triangles correspond to the average of the two individual rate measurements at each
temperature and the solid line (and equation with R2 value) is the best fit line through these data
points. This corresponds to the data given in Figure 4 of the manuscript. The horizontal lines above
and below each diamond correspond to the maximum and minimum value for that data point from
either of the individual rate measurements. The broken lines (and equations without R2 values)
correspond to the limiting values for the best fit line based on the error limits for the highest and
lowest temperature points. The data in Table 5 of the manuscript were obtained by averaging the
maximum and minimum values of Hǂ and S
ǂ obtained from the broken lines rather than from the
solid line so as to ensure that the quoted values were at the midpoint of the maximum and minimum
values.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
46
Addition of trimethylsilyl cyanide to benzaldehyde catalysed by Bu4NCN 4 (0.005 mol%)
Reaction at +20 oC run 1 Reaction at +20
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Reaction at +10 oC run 1 Reaction at +10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Reaction at 0 oC run 1 Reaction at 0
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
y = -0.00528x - 0.81552 R² = 0.99648
y = -0.00548x - 0.65714
y = -0.00515x - 0.75722
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 100 200 300 400 500 600 700
ln[P
hC
HO
]
Time (s)
y = -0.00577x - 0.75858 R² = 0.99718
y = -0.00602x - 0.65714
y = -0.00569x - 0.75722
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 100 200 300 400 500 600 700
ln[P
hC
HO
]
Time (s)
y = -0.00300x - 0.71317 R² = 0.99702
y = -0.00317x - 0.65714
y = -0.00284x - 0.75722
-3
-2.5
-2
-1.5
-1
-0.5
0
0 100 200 300 400 500 600 700
ln[P
hC
HO
]
Time (s)
y = -0.00271x - 0.72841 R² = 0.99760
y = -0.00278x - 0.65714
y = -0.00256x - 0.75722
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 200 400 600 800 1000
ln[P
hC
HO
]
Time (s)
y = -0.00123x - 0.72412 R² = 0.99770
y = -0.00129x - 0.65714
y = -0.00122x - 0.75722
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500
ln[P
hC
HO
]
Time (s)
y = -0.00153x - 0.73311 R² = 0.99875
y = -0.00159x - 0.65714
y = -0.00148x - 0.75722
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
47
Reaction at -10 oC run 1 Reaction at -10
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
Reaction at -20 oC run 1 Reaction at -20
oC run 2
The solid line, filled diamonds and equation with R
2 value correspond to the actual data and best fit
line whilst the empty squares and diamonds, broken line and equations without R2 values
correspond to a +/- 5% error applied to the absorbance of the first and last data points.
y = -0.00094x - 0.73729 R² = 0.99717
y = -0.00103x - 0.65714
y = -0.00087x - 0.75722
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400 600 800 1000 1200
ln[P
hC
HO
]
Time (s)
y = -0.00093x - 0.74566 R² = 0.99589
y = -0.00097x - 0.65714
y = -0.00088x - 0.75722
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500
ln[P
hC
HO
]
Time (s)
y = -0.00046x - 0.74116 R² = 0.99538
y = -0.00050x - 0.65714
y = -0.00043x - 0.75722
-2.5
-2
-1.5
-1
-0.5
0
0 500 1000 1500 2000 2500 3000
ln[P
hC
HO
]
Time (s)
y = -0.00049x - 0.68065 R² = 0.99872
y = -0.00051x - 0.65714
y = -0.00048x - 0.75722
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 1000 2000 3000 4000 5000 6000
ln[P
hC
HO
]
Time (s)
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
48
Eyring plot
y = -4.1806x + 3.2928R² = 0.9859
y = -4.6153x + 4.9454
y = -4.0103x + 2.7262
-13.5
-13.0
-12.5
-12.0
-11.5
-11.0
-10.5
3.4 3.5 3.6 3.7 3.8 3.9 4.0
ln(k
1o
bs/T
)
1000/T (K)
The filled triangles correspond to the average of the two individual rate measurements at each
temperature and the solid line (and equation with R2 value) is the best fit line through these data
points. This corresponds to the data given in Figure 4 of the manuscript. The horizontal lines above
and below each diamond correspond to the maximum and minimum value for that data point from
either of the individual rate measurements. The broken lines (and equations without R2 values)
correspond to the limiting values for the best fit line based on the error limits for the highest and
lowest temperature points. The data in Table 5 of the manuscript were obtained by averaging the
maximum and minimum values of Hǂ and S
ǂ obtained from the broken lines rather than from the
solid line so as to ensure that the quoted values were at the midpoint of the maximum and minimum
values.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
49
NMR stacked plots to investigate the formation of hypervalent silicon species
Addition of Et3N 1 to trimethylsilyl cyanide
1H NMR spectra
Bottom: 1H NMR spectrum of Me3SiCN.
Middle: 1H NMR spectrum of a 1:1 mixture of Me3SiCN and Et3N showing no change in the
position of the Me3SiCN signal and no new signals corresponding to the Me3Si groups of other
silicon containing species.
Top: 1H NMR spectrum of (Me3Si)2O
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012
-
50
13C NMR spectra
Bottom: 13
C NMR spectrum of Me3SiCN.
Middle: 13
C NMR spectru