Abstract
The reactions of Re2X4(μ-dppm)2 (X=Cl or Br; dppm=Ph2PCH2PPh2) with H2S in THF afford the dirhenium (III) complexes Re2(μ-H)(μ-SH)X4(μ-dppm)2, the first examples of the oxidative addition of an S-H unit across an electron-rich metal-metal triple bond. The bromide complex Re2(μ-H)(μ-SH)Br4(μ-dppm)2 (C2H5)2O crystallizes in the space group P21/n witha=16.631(2) Å,b=15.967(3) Å,c=19.904(2) Å, β=92.698(7)°,V=5279(2) Å3, andZ=4. The structure which was refined toR=0.053 (R w=0.070) for 4903 data withI>3.0σ(I), shows the presence of an edge-shared bioctahedral geometry with a very short Re-Re distance of 2.4566(7) Å. While the hydrogen atoms of the μ-H and μ-SH ligands were not located in the X-ray structure determination, their presence is confirmed by IR and1H NMR spectroscopy.
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References
F. A. Cotton and R. A. Walton,Multiple Bonds Between Metal Atoms (Wiley, New York, 1982) (The second edition of this text is currently in press—to be published by Oxford University Press).
F. A. Cotton and R. A. Walton (1985).Struct. Bonding (Berlin) 62, 1.
P. Brant, D. J. Salmon, and R. A. Walton (1978).J. Am. Chem. Soc. 100, 4424.
K. R. Dunbar and R. A. Walton (1985).Inorg. Chem. 24, 5.
R. A. Walton (1989).Polyhedron 8, 1689.
D. Esjornson, D. R. Derringer, P. E. Fanwick, and R. A. Walton (1989).Inorg. Chem. 28, 2821.
J.-S. Qi, P. W. Schrier, P. E. Fanwick, and R. A. Walton (1991).J. Chem. Soc. Chem. Commun. 1737;
J.-S. Qi, P. W. Schrier, P. E. Fanwick, and R. A. Walton (1992).Inorg. Chem. 31, 258.
A. Cutler, D. R. Derringer, P. E. Fanwick, and Rv. A. Walton (1988).J. Am. Chem. Soc. 110, 5024.
N. Walker and D. Stuart (1983).Acta Crystallogr. Sect. A: Found Crystallogr. A39, 158.
D. T. Cromer,International Tables for X-ray Crystallography (Kynoch, Birmingham, England, 1974), Vol. IV, Table 2.3.1.
For the scattering factors used in the structure solution see D. T. Cromer and F. T. Waber, —Ibid., Table 2.2B.
G. Besenyei, C.-L. Lee, J. Gulinski, S. J. Rettig, B. R. James, D. A. Nelson, and M. A. Lilga (1987).Inorg. Chem. 26, 3622.
D. M. Antonelli and M. Cowie (1990).Inorg. Chem. 29, 3339.
T. J. Barder, F. A. Cotton, D. Lewis, W. Schwotzer, S. M. Tetrick, and R. A. Walton (1984).J. Am. Chem. Soc. 106, 2882.
B. J. Heyen and G. L. Powell (1990).Inorg. Chem. 29, 4574.
S. J. Chen and K. R. Dunbar (1990).Inorg. Chem. 29, 529.
A preliminary report on some of these results has now been communicated: K.-Y. Shih, P. E. Fanwick and R. A. Walton (1992).J. Chem. Soc. Chem. Commun. 375.
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Shih, KY., Fanwick, P.E. & Walton, R.A. The oxidative addition of hydrogen sulfide to the electron-rich triple bond: The isolation and characterization of compounds that contain the Re2(μ-H)(μ-SH) cluster unit. J Clust Sci 2, 259–270 (1991). https://doi.org/10.1007/BF00702956
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DOI: https://doi.org/10.1007/BF00702956