Pd complex [(MeN2N)Pd(OTf)] (8). A solution of AgOTf (65 mg,
0.25 mmol) in THF (1.5 mL) was added to a solution of
[(MeN2N)PdCl] (100 mg, 0.25 mmol) in THF (2 mL). The resulting
solution was stirred for 30 min and then the white precipitate of
AgCl was filtered off. The filtrate was evaporated and the rose solid
residue was washed with pentane (3 mL) and dried under vacuum
(116 mg, 91%). Crystals suitable for X-ray diffraction analysis were
grown by diffusion of pentane to a benzene solution of 8. 1H NMR
(400.13 MHz, C6D6): 7.36 (d, J = 8.5 Hz, 2H), 6.85 (td, J = 8.5,
1.5 Hz, 2H), 6.37 (m, 4H), 2.66 (s, 12H). 13C NMR (100.62 MHz,
C6D6): 149.1, 146.3, 129.2, 121.4, 117. 9, 114.8, 52.1. Anal. Calcd
for C17H20F3N3O3PdS: C, 40.05; H, 3.95; N, 8.24. Found: C, 40.32;
H, 4.06; N, 8.15.
Notes and references
1 D. Morales-Morales and C. M. Jensen, ed., The chemistry of pincer
compounds, Elsevier, Amsterdam, 2007; M. E. van der Boom and D.
Milstein, Chem. Rev., 2003, 103, 1759–1792; J. I. van der Vlugt and
J. N. H. Reek, Angew. Chem., Int. Ed., 2009, 48, 8832–8846.
2 M. Albrecht and G. van Koten, Angew. Chem., Int. Ed., 2001, 40,
3750–3781.
3 L. C. Liang, Coord. Chem. Rev., 2006, 250, 1152–1177; O. V. Ozerov,
in The chemistry of pincer compounds, ed. D. Morales-Morales and
C. M. Jensen, Elsevier, Amsterdam, 2007, pp. 287–309.
4 L. C. Liang, J. M. Lin and C. H. Hung, Organometallics, 2003, 22,
3007–3009; L. C. Liang, P. S. Chien and Y. L. Huang, J. Am. Chem.
Soc., 2006, 128, 15562–15563; L. C. Liang, P. S. Chien, J. M. Lin,
M. H. Huang, Y. L. Huang and J. H. Liao, Organometallics, 2006, 25,
1399–1411.
5 L. C. Liang, J. M. Lin and W. Y. Lee, Chem. Commun., 2005, 2462–2464.
6 A. M. Winter, K. Eichele, H. G. Mack, S. Potuznik, H. A. Mayer and
W. C. K a s k a , J. Organomet. Chem., 2003, 682, 149–154.
7 L. Fan, B. M. Foxman and O. V. Ozerov, Organometallics, 2004, 23,
326–328.
8 O. V. Ozerov, C. Y. Guo, L. Fan and B. M. Foxman, Organometallics,
2004, 23, 5573–5580; L. Fan and O. V. Ozerov, Chem. Commun., 2005,
4450–4452; S. Gatard, R. Celenligil-Cetin, C. Y. Guo, B. M. Foxman
and O. V. Ozerov, J. Am. Chem. Soc., 2006, 128, 2808–2809.
9 D. Adhikari, S. Mossin, F. Basuli, J. C. Huffman, R. K. Szilagyi, K.
Meyer and D. J. Mindiola, J. Am. Chem. Soc., 2008, 130, 3676–3682;
J. G. Melnick, A. T. Radosevich, D. Villagran and D. G. Nocera, Chem.
Commun., 2010, 46, 79–81; K. Yurkerwich and G. Parkin, Inorg. Chim.
Acta, 2010, 364, 157–161.
Pt complex [(MeN2N)Pt(Cl)] (9). To a benzene (30 mL) suspen-
sion of Pt(PhCN)2Cl2 (687 mg, 1.46 mmol) was slowly added a
benzene (10 mL) solution of 6 (380 mg, 0.73 mmol). The reaction
mixture was stirred overnight at 80 ◦C, and then cooled to room
temperature and filtered through Celite. After removal of the
solvent, the oily residue was triturated with pentane which afforded
the product as an air-stable brown solid. This solid was dried in
vacuo. Yield: 495 mg (70%). Crystals suitable for X-ray analysis
were obtained by slow evaporation of a concentrated benzene
solution. 1H NMR (400.13 MHz, C6D6): 7.59 (dd, J = 8.5, 1.1 Hz,
2H), 6.95 (m, 2H), 6.52 (dd, J = 8.1, 1.4 Hz, 2H), 6.40 (m, 2H),
10 J. D. Masuda, K. C. Jantunen, O. V. Ozerov, K. J. T. Noonan, D. P.
Gates, B. L. Scott and J. L. Kiplinger, J. Am. Chem. Soc., 2008, 130,
2408–2409.
11 B. C. Bailey, J. C. Huffman and D. J. Mindiola, J. Am. Chem. Soc.,
2007, 129, 5302–5203; M. T. Whited and R. H. Grubbs, Acc. Chem.
Res., 2009, 42, 1607–1616.
1
2.99 (s, 12H). H NMR (400.13 MHz, CDCl3): 7.62 (dd, J =
8.2, 0.9 Hz, 2H), 7.15 (dd, J = 8.2, 1.2 Hz, 2H), 7.10 (m, 2H),
6.60 (m, 2H), 3.34 (s, 12H). 13C NMR (100.62 MHz, C6D6):
149.55, 149.22, 129.06, 121.81, 116.72, 114.81, 54.75. MALDI-
TOF: 485.10 [M+H]+. Anal. Calcd for C16H20ClN3Pt: C, 39.63; H,
4.16; N, 8.67. Found: C, 40.15; H, 4.36; N, 8.23.
12 E. Calimano and T. D. Tilley, J. Am. Chem. Soc., 2008, 130, 9226–9227.
13 R. J. Pearson, J. Am. Chem. Soc., 1963, 85, 3533–3539.
14 J. C. Peters, S. B. Harkins, S. D. Brown and M. W. Day, Inorg. Chem.,
2001, 40, 5083–5091.
Ru complex [(MeN2N)Ru(PPh3)Cl] (10). A THF solution (5 mL)
of Li complex 6 (200 mg, 0.38 mmol) was added to a THF
suspension (10 mL) of Ru(PPh3)3Cl2 (729 mg, 0.76 mmol). The
reaction mixture was stirred overnight at room temperature.
After removal of the solvent, the residue was taken up into
dichloromethane and filtered. The filtrate was evaporated, washed
with pentane, and dried under vacuum to give a green solid. Yield:
315 mg (63%). Crystals suitable for X-ray diffraction analysis were
grown by diffusion of pentane to a THF solution of 10. 1H NMR
(400.13 MHz, CDCl3): 7.47 (d, J = 8.4 Hz, 2H), 7.28–7.38 (m, 6H),
7.12–7.17 (m, 3H), 6.98–7.06 (m, 6H), 6.87–6.95 (m, 4H), 6.54 (t,
J = 7.6 Hz, 2H), 3.08 (s, 6H), 2.65 (s, 6H). 13C NMR (100.62 MHz,
THF-d8): 151.04, 138.09, 137.63, 134.32, 134.23, 129.15, 129.12,
127.85, 127.75, 126.55, 118.80, 117.57, 116.26, 51.67, 50.30.
31P NMR (162 MHz): 83.28. Anal. Calcd for C34H35N3ClPRu:
C, 62.52; H, 5.40; N, 6.43. Found: C, 62.86; H, 5.69;
N, 6.15.
15 T. A. Betley, B. A. Qian and J. C. Peters, Inorg. Chem., 2008, 47, 11570–
11582.
16 Z. Csok, O. Vechorkin, S. B. Harkins, R. Scopelliti and X. L. Hu, J. Am.
Chem. Soc., 2008, 130, 8156–8157.
17 O. Vechorkin, Z. Csok, R. Scopelliti and X. L. Hu, Chem.-Eur. J., 2009,
15, 3889–3899.
18 O. Vechorkin and X. L. Hu, Angew. Chem., Int. Ed., 2009, 48, 2937–
2940; O. Vechorkin, V. Proust and X. L. Hu, J. Am. Chem. Soc., 2009,
131, 9756–9766; O. Vechorkin, D. Barmaz, V. Proust and X. L. Hu,
J. Am. Chem. Soc., 2009, 131, 12078–12079; O. Vechorkin, V. Proust
and X. L. Hu, Angew. Chem., Int. Ed., 2010, 49, 3061–3064; X. L. Hu,
Chimia, 2010, 64, 231–234.
19 A. N. Marziale, E. Herdtweck, J. Eppinger and S. Schneider, Inorg.
Chem., 2009, 48, 3699–3709.
20 M. Q. Slagt, G. Rodriguez, M. M. P. Grutters, R. Gebbink, W. Klopper,
L. W. Jenneskens, M. Lutz, A. L. Spek and G. van Koten, Chem.-Eur. J.,
2004, 10, 1331–1344.
21 J. Breitenfeld, O. Vechorkin, C. Corminboeuf, R. Scopelliti and X. L.
Hu, Organometallics, 2010, 29, 3686–3689.
22 P. Dani, T. Karlen, R. A. Gossage, S. Gladiali and C. van Koten, Angew.
Chem., Int. Ed., 2000, 39, 743–745.
23 F. L. Zeng and Z. K. Yu, Organometallics, 2008, 27, 2898–2901; M. J.
Page, J. Wagler and B. A. Messerle, Organometallics, 2010, 29, 3790–
3798.
24 A. P. Shaw, B. L. Ryland, J. R. Norton, D. Buccella and A. Moscatelli,
Inorg. Chem., 2007, 46, 5805–5812.
25 G. M. Sheldrick, Bruker AXS Inc., Madison, Wisconsin, 53719, USA,
2003.
26 H. T. N. Thi, C. Y. Lee, K. Teruya, W. Y. Ong, K. Doh-Ura and M. L.
Go, Bioorg. Med. Chem, 2008, 16, 6737–6746.
27 G. D. Vo and J. F. Hartwig, J. Am. Chem. Soc., 2009, 131, 11049–
11061.
28 W. Levason, K. G. Smith, C. A. McAuliffe, F. P. McCullough, R. D.
Sedgwick and S. G. Murray, J. Chem. Soc., Dalton Trans., 1979, 1718–
1724.
General procedure for transfer hydrogenation catalysis.
A
freshly prepared dichloromethane solution of 10 (2 mmol,
0.2 mol%) was evaporated under vacuum in a three-necked flask.
Next, ketone (1 mmol) was added to the flask under nitrogen,
followed by 9.75 mL of 2-propanol. The mixture was heated to
83 ◦C, and then it was treated with 0.2 M KOH in 2-propanol
(0.25 mL), initiating the reaction (t = 0). During the course of
the reaction, an aliquot (0.20 mL) solution was removed from the
reaction mixture via a syringe, diluted with 5 mL of diethyl ether,
and cooled to room temperature. The sample was analyzed via
GC. The products were identified by GC-MS.
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The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 8906–8911 | 8911
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