Tridentate and tetradentate iminophosphorane-based ruthenium complexes in catalytic transfer hydrogenation of ketones

Article abstract of DOI:10.1021/om101058m

Tetradentate iminophosphorane complexes [RuH(PNNP)][BAr^F ₄] (5) and [RuHCl(PNNP)] (6) (PNNP = PPh₂CH ₂PPh₂NCH₂CH₂NPPh₂CH ₂PPh₂), prepared by in s

Full text of DOI:10.1021/om101058m

Supplementary Material
Tridentate and Tetradentate
Iminophosphorane-Based Ruthenium
Complexes in Catalytic Transfer Hydrogenation
of Ketones.
Hellen Dyer,† Alexandre Picot,† Laure Vendier,† Audrey Auffrant,‡ Pascal Le Floch‡
and Sylviane Sabo-Etienne.†*
†CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, F-31077
Toulouse, France, Université de Toulouse, UPS, INPT, F-31077 Toulouse, France,
‡Laboratoire Hétéroélements et Coordination, Ecole Polytechnique, CNRS, 91128 Palaiseau
Cedex, France.
E-mail: sylviane.sabo@lcc-toulouse.fr
S1

Table of Contents
1. Figure S1: Conversion of acetophenone, expressed as a percentage yield, as a function of
time with 6.................................................................................................................................. 3
2. Figure S2: Graph of ln(K/T) vs 1/T with 6........................................................................ 3
3. Figure S3: Schematic representation of a postulated intermediate.................................... 4
4. Table S1. Influence of PCy3 on the catalytic hydrogenation of acetophenone with 6 as
precatalyst................................................................................................................................... 4
5. Complete Gaussian reference .......................................................................................... 4
6. ONIOM optimisation for 7 and Cartesian coordinates................................................. 6
S2

1. Figure S1: Conversion of acetophenone, expressed as a percentage yield, as a
function of time with 6.
100
90
80
70
60
50
40
30
20
10
0
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
Time (sec)
2. Figure S2: Graph of ln(K/T) vs 1/T with 6.
0,003 0,003 0,003 0,003 0,003 0,003 0,003 0,003
-13,6
-14,1
y = -6676,3x + 5,3431
R2 = 0,9988
-14,6
-15,1
-15,6
1/T (K-1)
S3

3. Figure S3: Schematic representation of a postulated intermediate.
In light of the similar kinetics and chemeoselectivity observed for 6 and 3 one could
postulate an outer sphere hydride transfer assisted by the ligand, with reformation of the Ru-H
facilitated by the presence of the isoproxide anion in solution. Unfortunately evidence of the
formation of a P-OiPr functionality could not be detected spectroscopically (31P and 1H NMR
where applicable) at ambient temperature or at 345K upon stoichiometric reaction of 5 and 6
with excess NaOiPr in THF-d8 and in iPrOH.
4. Table S1. Influence of PCy3 on the catalytic hydrogenation of acetophenone with 6
as precatalyst.
Conversion (%)
Entry
1a
20 min
38
40 min
58
60 min
68
80 min
76
120 min
87
2b
32
57
72
81
91
a
Conditions: 100 equiv of acetophenone (146 µL, 1.25 mmol), 10 equiv Na (2.9 mg,
0.125 mmol), 100 equiv of the internal standard veratrole (160 µL, 1.25 mmol) and 1
i
equiv of 6 (0.0125 mmo) in 5 mL of PrOH at 80 ºC.b Conditions: same as for those
for footnote a but with the addition of 10 equivalents of PCy3.
5. Complete Gaussian reference
Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J.
C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani,
G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.;
Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts,
S4

R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.;
Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.;
Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.;
Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R.
L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.;
Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.;
Gaussian, Inc., Wallingford CT, 2004
S5

6. ONIOM optimisation for 7 and Cartesian coordinates.
In the structure below the MM part is represented with tubes whereas the MQ part with ball
and bonds.
---------------------------------------------------------------------
Center
Number
---------------------------------------------------------------------
Atomic
Atomic
Coordinates (Angstroms)
Number
Type
X
Y
Z
1
2
6
1
1
6
6
1
1
1
6
1
1
1
6
1
1
1
6
1
1
6
10061003
10011000
10011000
10061003
10061003
10011000
10011000
10011000
10061003
10011000
10011000
10011000
10061003
10011000
10011000
10011000
10061003
10011000
10011000
10061003
-2.886584 -1.577216 -2.268543
-3.816417 -2.163493 -2.323450
-2.064937 -2.275796 -2.464517
-2.932039 -0.515784 -3.393183
3
4
5
-1.614456
-1.361290
-1.679373
0.260513 -3.445888
0.701668 -2.456759
1.108713 -4.138345
6
7
8
-0.776247 -0.377921 -3.737723
-3.117897 -1.262701 -4.723135
-2.308547 -1.982926 -4.893787
-3.125753 -0.561596 -5.566066
-4.068251 -1.810655 -4.741246
9
10
11
12
13
14
15
16
17
18
19
20
-4.100966
-5.062862 -0.076692 -3.213556
-4.122837 1.215984 -3.966780
-4.019672 0.964835 -2.217282
3.772237 -2.893573 0.467198
4.826557 -2.654728 0.660454
3.742415 -3.572948 -0.397780
3.196140 -3.625028 1.694672
0.450920 -3.181795
S6

21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
6
1
1
1
6
1
1
1
6
1
1
1
6
6
1
6
1
6
1
6
1
6
1
6
6
1
6
1
6
1
6
1
6
1
6
6
1
6
1
6
1
6
1
6
1
6
6
1
6
1
6
1
6
1
6
1
6
6
1
6
1
10061003
10011000
10011000
10011000
10061003
10011000
10011000
10011000
10061003
10011000
10011000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
3.967756 -4.949877
3.620703 -5.521023
5.045046 -4.781907
3.821548 -5.576523
1.704996 -3.913204
1.518123 -4.472918
1.108429 -2.993984
1.332184 -4.514068
3.393538 -2.813398
2.868929 -1.854161
4.455546 -2.623154
2.993590 -3.365585
1.802022
2.670290
1.927574
0.913681
1.492152
0.567723
1.456893
2.329590
2.979413
2.933333
3.180412
3.837549
-5.315854 -1.764889 -0.160087
-6.226533 -0.815601 -0.651479
-5.953935 0.226239 -0.741980
-7.501355 -1.219961 -1.053373
-8.208550 -0.494188 -1.433424
-7.854545 -2.568660 -0.969599
-8.839723 -2.891040 -1.280932
-6.928712 -3.504104 -0.492830
-7.205066 -4.549650 -0.441358
-5.700096 -3.118927 -0.105688
-5.006739 -3.872786
-3.026909 -2.537449
-2.063844 -3.454513
-1.653693 -3.382378
-1.646148 -4.494960
-0.919958 -5.212012
-2.144402 -4.617289
-1.807596 -5.424823
-3.108697 -3.718526
-3.515123 -3.835120
-3.563413 -2.684561
-4.338594 -2.021109
0.242002
1.446555
1.002707
0.004303
1.842702
1.483373
3.084608
3.722066
3.557307
4.553558
2.733574
3.092600
0.263107
-2.855856
-2.618356
-1.999570
-3.185949
-2.986533
-3.973195
-4.403504
-4.249055
-4.892132
-3.698717
-3.926028
-1.454831
-1.055322
-1.154851
-0.523443
-0.216647
-0.388706
0.024203
2.802224
3.252007 -1.040814
2.683371 -1.711321
4.451076 -1.490628
4.790429 -2.499172
5.181614 -0.683604
6.106821 -1.045107
4.752655
5.342914
3.557613
3.225059
1.580955
2.880069
3.702537
3.132096
4.134864
2.092485
2.289356
0.796292
0.620480
1.260310
1.093310
2.098105
2.491715
2.848244
2.156619
4.116285
4.383787
5.039356
6.020081
4.691208
5.401484
3.420903
3.161411
-0.775413
-0.659556 -0.011966
-1.298690 0.539558
-1.576071 -0.473467
0.787981
0.699660
0.848413
0.401463
0.337638
2.827010 -1.229846
2.954019 -2.624670
2.099510 -3.270568
4.199645 -3.193012
4.293956 -4.269527
S7

82
83
6
1
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061003
10011000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061000
10011000
10061003
10011000
10011000
10071002
10071002
10011000
10151004
10151003
10151003
10151004
10441006
10171000
10011000
0.186764
-0.045678
0.243607
0.053008
0.532308
0.548689
1.940813
1.770575
5.276092 -2.413507
6.228274 -2.873679
5.186700 -1.071474
6.063190 -0.465396
3.965269 -0.448616
84
6
85
1
86
6
87
1
3.917733
1.597031
0.775471
0.628258
1.112238
2.234548
2.187883
3.431431
4.292934
3.518188
4.449602
2.404163
2.472834
1.193622
0.327879
88
6
89
6
90
1
1.144063 -0.099508
91
6
2.440916
2.291013
3.271942
3.783114
3.507542
4.206214
2.864220
3.093397
2.639591
2.224787
3.235264
5.070399
5.276667
1.061799
0.423728
2.112681
2.319423
2.925661
3.749240
2.653911
3.260513
92
1
93
6
94
1
95
6
96
1
97
6
98
1
99
6
0.704377 -1.506785
0.330719 -2.446654
1.597815 -1.728285
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
1
1
6
0.350791
0.164295
0.012379
1.386878
1.953624
2.042640
3.104526
1.359889
1.873538
6
1
4.663063 -0.515699
6
6.276102
6.434007
7.028970
7.797145
6.824726
7.438748
5.874244
5.735053
0.892346
0.753398
1.771300
2.335156
1
6
1
6
1.968034 -0.014715
2.680921 -0.550106
1.279648 -0.670867
1.445313 -1.731911
1
6
1
6
4.590312 -1.395931 -2.259764
5.957332 -1.717550 -2.207049
6.557193 -1.453674 -1.346621
6.562659 -2.402459 -3.268893
7.618251 -2.637757 -3.219979
5.845654 -2.776143 -4.341670
6.327531 -3.307225 -5.152688
4.476085 -2.496025 -4.415552
3.904315 -2.815372 -5.277315
3.844016 -1.813480 -3.371835
2.781287 -1.631085 -3.433420
6
1
6
1
6
1
6
1
6
1
6
-3.745002
-3.842633
-4.623126
0.297518
0.138588
0.865543
1.290127
2.366649
0.976417
1
1
7
-2.701919 -0.994628 -0.934787
3.054876 -1.639887 0.118973
2.083384 -1.811978 -0.207374
-3.646850 -1.261559 0.329725
-2.162110 1.209274 0.844259
1.117728 1.182692 -0.478216
7
1
15
15
15
15
44
17
1
3.784806 -0.551833 -0.874198
-0.825568 -0.012391 -0.496998
0.427201 -1.798886 -1.639504
-0.458465 -0.736840
0.831078
S8