TY - JOUR
T1 - Structural studies of binuclear suiphido-bridged complexes of tungsten. Preparation and X-ray crystal structures of [S2W(μ-S)2W(NNMe2)2(PPh 3)] and [{W(SBut)2(PMe2Ph)}2(μ-S) 2]·CH2Cl2
AU - Dilworth, Jonathan R.
AU - Richards, Raymond L.
AU - Dahlstrom, Phillip
AU - Hutchinson, John
AU - Kumar, Surendra
AU - Zubieta, Jon
N1 - Funding Information:
Similarly, the Mo-Mo distances of [{Mo(SBu')2-(PMe2Ph))2(p-S),] [2.741(1) A] and [{MO(SBU'),(NHM~~))~-(p-S)J [2.730( 1) A] are significantly shorter than that observedfor the molybdenum analogue of (l), [S,MOS,MO(NNM~~)~-(PPh3)] [3.005(2) A].13AcknowledgementsThis research was supported in part by N.I.H. grants. J. R. D.and J. Z. are indebted t o N.A.T.O. for award of a travel grant.References1 ' Molybdenum and Molybdenum-Chemistry Enzymes,' ed.2 A. Muller, E. Diemann, R. Josten, and H. Bogge, Angew.3 T. Higuchi, K. Hirotsu, M. Kamata, S. Otsuka, and T. Yoshida,M. P. Coughlin, Pergarnon Press, Oxford, 1980.Chem., Int. Ed. Engl., 1981, 20, 934.J. Am. Chem. Soc,, 1981,103, 3572.4 P. M. Boorman, K. A. Kev, and V. D. Patel, J. Chern. SOC.,Dalton Trans., 1981, 506.5 J. Chatt, J. P. Lloyd, and R. L. Richards, J. Chem. Soc., DaltonTrans., 1976, 565.6 J. Chatt, A. J. Pearman, and R. L. Richards, J. Chem. Soc.,Dalton Trans., 1977, 1852.7 B. A. L. Crichton, J. R. Dilworth, P. Dahlstrom, and J. Zubieta,Transition Met. Chem., 1980, 5, 316.8 T. E. Wolff, J. M. Berg, K. 0. Hodgson, R. B. Frankel, andR. H. Holm, J. Am. Chern. SOC., 1979, 101,4140.9 D. T. Cromer and J. B. Mann, Acta Crystallogr., Secf. A ,1968, 24, 321.10 ' International Tables for X-Ray Crystallography,' KynochPress, Birmingham, 1962, vol. 3.11 G. M. Sheldrick, in ' Nicolet SHELXTL Operation Manual,'Nicolet XRD Corporation, Cupertino, CA, 1979.12 See, for example, J. Chatt, B. A. L. Crichton, J. R. Dilworth,P. Dahlstrom, R. Gutkoska, and J. A. Zubieta, TransitionMet. Chem., 1979,4, 271.13 J. R. Dilworth and J. A. Zubieta, J. Chem. SOC., Chem. Corn-mun., 1981, 132.14 M. H. Chisholm, J. F. Corning, and J. C. Huffman, Inorg.Chem., 1982,21,296.Received 23vd August 1982; Paper 21146
PY - 1983
Y1 - 1983
N2 - The reaction of [NBun4]2[WS4] with [WCl(NNMe2)2(PPh3)2]Cl yields the asymmetric binuclear complex [S2W(μ-S)2W(NNMe2)2(PPh 3)] (1). Complex (1) crystallizes in space group Cc, with a = 15.389(2), b = 10.292(4), c = 18.406(2) Å, β = 90.43(1)°, and Z = 4; final R = 0.061 based on 4 091 reflections collected, 2 116 used. One tungsten is trigonally pyramidally co-ordinated with two NNMe2 groups in the equatorial plane and one axial and one equatorial bridging sulphide with a W-W separation of 3.024(1) Å. The reaction of cis-[W(N2)2(PMe2Ph)4] with ButSH gives the symmetric binuclear complex [{W(SBut)2(PMe2Ph)}2(μ-S) 2] (2). Complex (2) crystallises in space group P1̄, with a = 9.654(4), b = 10.331(4), c = 13.288(5) Å, α = 78.09(1), β = 69.36(1), γ = 82.49(1)°, and Z = 1; final R = 0.071 based on 4 732 reflections collected, 2 310 used. The centre of symmetry imposes planarity on the W2S2 system with a W-W distance of 2.736(2) Å. Each tungsten has distorted trigonal-bipyramidal geometry with bridging sulphide and phosphorus in the apical sites.
AB - The reaction of [NBun4]2[WS4] with [WCl(NNMe2)2(PPh3)2]Cl yields the asymmetric binuclear complex [S2W(μ-S)2W(NNMe2)2(PPh 3)] (1). Complex (1) crystallizes in space group Cc, with a = 15.389(2), b = 10.292(4), c = 18.406(2) Å, β = 90.43(1)°, and Z = 4; final R = 0.061 based on 4 091 reflections collected, 2 116 used. One tungsten is trigonally pyramidally co-ordinated with two NNMe2 groups in the equatorial plane and one axial and one equatorial bridging sulphide with a W-W separation of 3.024(1) Å. The reaction of cis-[W(N2)2(PMe2Ph)4] with ButSH gives the symmetric binuclear complex [{W(SBut)2(PMe2Ph)}2(μ-S) 2] (2). Complex (2) crystallises in space group P1̄, with a = 9.654(4), b = 10.331(4), c = 13.288(5) Å, α = 78.09(1), β = 69.36(1), γ = 82.49(1)°, and Z = 1; final R = 0.071 based on 4 732 reflections collected, 2 310 used. The centre of symmetry imposes planarity on the W2S2 system with a W-W distance of 2.736(2) Å. Each tungsten has distorted trigonal-bipyramidal geometry with bridging sulphide and phosphorus in the apical sites.
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U2 - 10.1039/DT9830001489
DO - 10.1039/DT9830001489
M3 - Article
AN - SCOPUS:37049098066
SN - 1472-7773
SP - 1489
EP - 1493
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 8
ER -