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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

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011

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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).


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