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Electronic Supplementary Information
The Effects of Ligand Variation on Enantioselective Hydrogenation
Catalysed by Ru(H)2(diphosphine)(diamine) Complexes
Hsin-Yi Tiffany Chen*, Devis Di Tommaso, Graeme Hogarth, and C. Richard A. Catlow
Department of Chemistry, Christopher Ingold Laboratories, University College London, 20 Gordon Street, London, WC1H 0AJ, United Kingdom
* Authors to whom correspondence should be addressed. E-mail: [email protected]
Contents
Scheme S1 The asymmetric acetophenone hydrogenation catalysed by the RuH2(diphosphine)(diamine)] complexes considered in the present study ....................................... 2
Figure S1 The structures in the asymmetric hydrogenation of acetophenone catalysed by the RuH2[(S)-XylBINAP][(S,S)-DPEN] in the Pre-INT, INT, TS and PRO along the Q1, Q2, Q3, and Q4 pathways. (Pre-INT is the slightly less stable intermediate before forming the most stable intermediate; INT is the most stable intermediate; TS is the transition state; PRO = [Phenylethanol + 16e– Ru species]; The arrows stand for the repulsion between ACP and the catalyst). ................. 3
Figure S3 The structures in the Pre-INT, INT, TS and PRO in the hydrogenation of acetophenone (ACP) along Q1 and Q2 in [ACP + 1a/2a], [ACP + 1b/2a], and [ACP + 1c/2a]. ............................ 5
Figure S4 Comparison of structural variation in the asymmetric hydrogenation of acetophenone catalysed by the RuH2[(S)-TolBINAP][(R)-DMAPEN] and RuH2[(S)-XylBINAP][(S,S)-DPEN] along the Q3 pathway. ....................................................................................................................... 7
Figure S5 Comparison of structural variation in the asymmetric hydrogenation of acetophenone catalysed by the RuH2[(S)-TolBINAP][(R)-DMAPEN] and RuH2[(S)-XylBINAP][(R)-DPEN] along the Q4 pathway. ....................................................................................................................... 7
Table S1 Energetical characteristics of asymmetric hydrogenation of acetophenone in the INT, TS and PRO in [1a/2a], [1a/2b] and [1a/2d]. ......................................................................................... 8
Figure S6 The structural characteristics in the hydrogenation of acetophenone in the INT, TS and PRO in [1a/2a], [1a/2b], and [1a/2d] (top view). ............................................................................. 9
Figure S7 The structural characteristics in the hydrogenation of acetophenone in the INT, TS and PRO in [1a/2a], [1a/2b], and [1a/2d] (side view). .......................................................................... 10
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All of the systems are labelled according to the Scheme S1.
(R1)2N
NH2
H
H
H
H
Ar2P
PAr2
Ru
R2
R3
Ar = 3,5-(CH3)2C6H3; (S)-XylBINAP 1a R1=H, R2=R3=Ph; (S,S)-DPEN 2a
Ar = 4-(CH3)C6H4; (S)-TolBINAP 1b R1=CH3, R2=R3=Ph; (S,S)-DMDPEN 2b
Ar = C6H5; (S)-BINAP 1c R1=CH3, R2=H, R3=Ph; (S)-DMAPEN 2c
R1=CH3, R2=H, R3=Ph; (R)-DMAPEN 2d
(The DMAPEN shown here is S-configuration.)
O OH
[Cat]H2
ACP
[Cat] =
Scheme S1 The asymmetric acetophenone hydrogenation catalysed by the
RuH2(diphosphine)(diamine)] complexes considered in the present study
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Figure S2 The structures in the asymmetric hydrogenation of acetophenone catalysed by the
RuH2[(S)-XylBINAP][(S,S)-DPEN] in the Pre-INT, INT, TS and PRO along the Q1, Q2, Q3, and Q4
pathways. (Pre-INT is the slightly less stable intermediate before forming the most stable
intermediate; INT is the most stable intermediate; TS is the transition state; PRO = [Phenylethanol +
16e– Ru species]; The arrows stand for the repulsion between ACP and the catalyst).
Q1-(R) Q2-(S) Q3-(S) Q4-(R)
Pre-INT
INT ─
─
TS
PRO
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Figure S2 The structures in the asymmetric hydrogenation of acetophenone catalysed by the
RuH2[(S)-XylBINAP][(S,S)-DPEN] in the Pre-INT along the Q1, Q2, Q3, and Q4 pathways (Figure
S2 magnifies the structures in first row, Pre-INT, in Figure S1.).
Pre-INT
Q1-(R)
Q2-(S)
Q3-(S)
Q4-(R)
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Path Pre-INT INT TS PRO
1a/
2a Q1
1b/
2a Q1
1c/
2a Q1
1a/
2a Q2
─
1b/
2a Q2
─
1c/
2a Q2
─
Figure S3 The structures in the Pre-INT, INT, TS and PRO in the asymmetric hydrogenation of
acetophenone (ACP) along Q1 and Q2 in [ACP + 1a/2a], [ACP + 1b/2a], and [ACP + 1c/2a].
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Q3 1b/2d 1b/2d 1a/2a 1a/2a
top view side view top view side view
5
Å ─ ─
3.5
Å
1.8
5
Å
TS
PR
O
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Figure S4 Comparison of structural variation in the asymmetric hydrogenation of acetophenone
catalysed by the RuH2[(S)-TolBINAP][(R)-DMAPEN] and RuH2[(S)-XylBINAP][(S,S)-DPEN]
along the Q3 pathway.
Q4 1b/2d 1b/2d 1a/2a 1a/1b
top view side view top view side view
3.3
Å
1.85
Å
TS
PR
O
Figure S5 Comparison of structural variation in the asymmetric hydrogenation of acetophenone
catalysed by the RuH2[(S)-TolBINAP][(R)-DMAPEN] and RuH2[(S)-XylBINAP][(R)-DPEN] along
the Q4 pathway.
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Table S1 Energetical characteristics of asymmetric hydrogenation of acetophenone in the INT, TS
and PRO in [1a/2a], [1a/2b] and [1a/2d].
System Whole System
path INT TS Ea ΔEa ee
kcal/mol [%]
1a/2a Q1 -3.16 -1.82 1.34
5.31 97-99 Q2 -4.37 2.29 6.65
1a/2b Q1 -2.66 6.96 9.62
1.71 ─ Q2 -1.30 10.04 11.33
1a/2c Q1 -2.15 6.10 8.35
1.86 ─ Q2 -1.59 8.62 10.21
• Ea represents the activation energy
• ΔEa represents the difference in activation energy ( Here, ΔEa = Ea, Q2 – Ea, Q1)
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Path Pro-INT INT TS PRO
1a/2a Q1
1a/2b Q1
─
1a/2d Q1
─
1a/2a Q2
─
1a/2b Q2
─
1a/2d Q2
─
Figure S6 The structural characteristics in the asymmetric hydrogenation of acetophenone in the INT,
TS and PRO in [1a/2a], [1a/2b], and [1a/2d] (top view).
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Path Pro-INT INT TS PRO
1a/2a Q1
1a/2b Q1 ─
1a/2d Q1
─
1a/2a Q2
─
1a/2b Q2
─
1a/2d Q2
─
Figure S7 The structural characteristics in the asymmetric hydrogenation of acetophenone in the INT,
TS and PRO in [1a/2a], [1a/2b], and [1a/2d] (side view).
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011