Communications
[1]R. H. Morris, P. G. Jessop, Coord. Chem. Rev. 1992, 121, 155 –
284.
[2]a) B. Chaudret, R. Poilblanc, Organometallics 1985, 4, 1722 –
1726; b) S. Sabo-Etienne, B. Chaudret, Coord. Chem. Rev.
1998, 178–180, 381 – 407.
[3]F. Kakiuchi, S. Murai, Acc. Chem. Res. 2002, 35, 826 – 834.
[4]a) J. T. Golden, R. A. Andersen, R. G. Bergman, J. Am. Chem.
Soc. 2001, 123, 5837 – 5838; b) S. R. Klei, J. T. Golden, T. D.
Tilley, R. G. Bergman, J. Am. Chem. Soc. 2002, 124, 2092 – 2093;
c) S. R. Klei, T. D. Tilley, R. G. Bergman, Organometallics 2002,
21, 4905 – 4911; d) M. R. Skaddan, C. M. Yung, R. G. Bergman,
Org. Lett. 2004, 6, 11 – 13; e) C. M. Yung, M. R. Skaddan, R. G.
Bergman, J. Am. Chem. Soc. 2004, 126, 13033 – 13043.
[5]A. F. Thomas, Deuterium Labelling in Organic Chemistry,
Meridith Cooperation, New York, 1971.
[6]T. H. Lowry, K. S. Richardson, Mechanism and Theory in
Organic Chemistry, Harper and Row, New York, 1987.
[7]M. Yamamoto, Y. Yokota, K. Oshima, S. Matsubara, Chem.
Commun. 2004, 1714 – 1715.
[8]B. Rybtchinski, R. Cohen, Y. Ben-David, J. M. L. Martin, D.
Milstein, J. Am. Chem. Soc. 2003, 125, 11041 – 11050.
[9]a) C. P. Lenges, P. S. White, M. Brookhart, J. Am. Chem. Soc.
1999, 121, 4385 – 4396; b) B. McAuley, M. J. Hockey, L. P.
Kingston, J. R. Jones, W. J. S. Lockley, A. N. Mather, E. Spink,
S. P. Thompson, D. J. Wilkinson, J. Labelled Compd. Radio-
pharm. 2003, 46, 1191 – 1204; c) J. Krüger, B. Manmontri, G. Fels,
Eur. J. Org. Chem. 2005, 1402 – 1408; d) Q.-X. Guo, B.-J. Shen,
H.-Q. Guo, T. Takahashi, Chin. J. Chem. 2005, 23, 341 – 344.
[10]D. Giunta, M. Hꢁlscher, C. W. Lehmann, R. Mynott, C. Wirtz,
W. Leitner, Adv. Synth. Catal. 2003, 345, 1139 – 1145.
[11]a) S. Busch, W. Leitner, Chem. Commun. 1999, 2305 – 2306;
b) M. H. G. Prechtl, Y. Ben-David, D. Giunta, S. Busch, Y.
Taniguchi, W. Wisniewski, H. Gꢁrls, R. J. Mynott, N. Theyssen,
D. Milstein, W. Leitner, Chem. Eur. J. 2006, DOI: 10.1002/
chem.200600897.
Scheme 5. Relative energies (DH, DH°; DG, DG° (in italics), kcal
molÀ1) of reactants, products, and transition states (not shown)
À
involved in C H exchange at the ortho, meta, and para positions
(top to bottom) of toluene.
In summary, we have shown that the nonclassical ruthe-
nium hydride complex 1 is an effective catalyst for H/D
exchange between aromatic substrates and D2O under
unprecedented mild conditions. The incorporation occurs
with aromatic and heteroaromatic substrates, with significant
chemo- and regioselectively observed in certain cases. DFT
calculations support a catalytic cycle comprising s-bond
metathesis as the key step for the exchange processes and
with a strong steric component directing the effect. Further
preparative and mechanistic studies to explore the catalytic
potential of 1 and related complexes are underway.
[12]a) P. Foley, R. DiCosimo, G. M. Whitesides, J. Am. Chem. Soc.
1980, 102, 6713 – 6725; b) G. M. Whitesides, M. Hackett, R. L.
Brainard, J.-P. P. M. Lavalleye, A. F. Sowinski, A. N. Izumi, S. S.
Moore, D. W. Brown, E. M. Staudt, Organometallics 1985, 4,
1819 – 1830; c) C. Paal, W. Hartmann, Ber. Dtsch. Chem. Ges.
1918, 51, 711 – 737.
À
[13]For a recent experimental and computational study on H
X
bond activation (X = O and C), see S. L. Chatwin, M. G.
Davidson, C. Doherty, S. M. Donald, R. F. R. Jazzar, S. A.
Macgregor, G. J. McIntyre, M. F. Mahon, M. K. Whittlesey,
Organometallics 2006, 25, 99 – 110.
[8]
À
[14]Related C H activation mechanisms were described for Rh
and Ir complexes: E. Ben-Ari, R. Cohen, M. Gandelman,
L. J. W. Shimon, J. M. L. Martin, D. Milstein, Organometallics
2006, 25, 3190 – 3210.
Received: September 8, 2006
Revised: January 15, 2007
Published online: February 15, 2007
À
[15]C H activation of arenes with subsequent H transfer to olefins
has been described for Ru complexes: a) M. Lail, C. M. Bell, D.
Conner, T. R. Cundari, T. B. Gunnoe, J. L. Petersen, Organo-
metallics 2004, 23, 5007 – 5020; b) H. Weissman, X.-P. Song, D.
Milstein, J. Am. Chem. Soc. 2001, 123, 337 – 338.
À
Keywords: C H activation · density functional calculations ·
H/D exchange · homogeneous catalysis · ruthenium
.
2272
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 2269 –2272