99808-51-2Relevant academic research and scientific papers
A Series of Edge-Sharing Bioctahedral, M-M Bonded Molecules: Non-Monotonic Bond Length Variation and Its Interpretation
Chakravarty, Akhil R.,Cotton, F. Albert,Diebold, Michael P.,Lewis, Diane B.,Roth, Wieslaw J.
, p. 971 - 976 (1986)
Three new stoichiometrically homologous compounds, Ta2Cl6(dmpm)2 (1), Mo2Cl6(dppm)2 (2) Ru2Cl6(dmpm)2 (3) have been prepared and their structures determined.Crystal data are as follows. 1: P21/n, a = 7.263(3) Angstroem, b = 15.536(3) Angstroem, c = 10.827(2) Angstroem, β = 93.73(2) deg, V = 1219(1) Angstroem3, Z = 2. 2: C2/c, a = 23.083(4) Angstroem, b = 10.866(4) Angstroem, c = 23.254(5) Angstroem, β = 124.25(3) deg, V = 4821(4) Angstroem3, Z = 4. 3: I2/a, a = 12.479(5) Angstroem, b = 15.330(6) Angstroem, c = 13.212(4) Angstroem, β = 113.91(3) deg, V = 2310(1) Angstroem3, Z = 4.These three compounds, as well as the previously described Nb2Cl6(dmpm)2 and Re2Cl6(dppm)2,consist of molecules in which two octahedra share an edge via μ-Cl atoms, thus forming a central, planar Cl2M(μ-Cl)2MCl2 unit with dridging dmpm or dppm molecules connecting pairs of adjacent axial positions above and below the central plane.The M-M distances in these five molecules are the following: Nb-Nb, 2.711(3) Angstroem; Ta-Ta, 2.692(2) Angstroem; Mo-Mo, 2.789(1) Angstroem; Re-Re, 2.616(1) Angstroem; Ru-Ru, 2.933(1) Angstroem.The up, down, up variation on proceeding through the d2-d2, d3-d3, d4-d4, d5-d5 series of metal atom pairs is consistent with the following electronic configurations: ?2?2, ?2?2δ*2, ?2?2δ*2δ2?*2.The relationship of this structurally indicated ordering of the orbitals is discussed in the light of molecular quantum mechanical calculations on model systems, and it is shown that the overall experimental and theoretical picture is internally consistent.
Oxidative-addition reactions of S-S and Se-Se bonds to Mo2 and W2 quadruple bonds
Canich, Jo Ann M.,Albert Cotton,Dunbar, Kim R.,Falvello, Larry R.
, p. 804 - 811 (2008/10/08)
Oxidative-addition chemistry of the quadruply bonded molybdenum and tungsten M2Cl4(dppm)2 dimers (dppm = bis(diphenylphosphino)methane) has been investigated by using diphenyl disulfide, diphenyl diselenide, dichloromethane, and chlorine as the oxidizing agents. The products to be discussed here are the following: W2(μ-SPh)2Cl4(dppm)2 (1), W2(μ-SPh)(μ-Cl)-Cl4(dppm)2 (2), W2(μ-SePh)2Cl4(dppm)2 (3), W2(μ-SePh)(μ-Cl)Cl4(dppm)2 (4), W2(μ-Cl)2Cl4(dppm)2 (5), Mo2(μ-SPh)(μ-Cl)Cl4(dppm)2 (6), and Mo2(μ-Cl)2Cl4(dppm)2 (7). The structural characterization of compounds 1, 4, and 6 is reported here. Pertinent crystal data are as follows: 1, P1, a = 12.991 (2) A?, b = 13.851 (3) A?, c = 11.693 (2) A?, α = 111.28 (2)°, β = 103.43 (2)°, γ = 89.03 (2)°, V = 1903 (1) A?3, W-W = 2.787 (1) A?; 4, Pna21, a = 39.335 (10) A?, b = 15.371 (4) A?, c = 11.774 (3) A?, V = 7119 (5) A?3, W-W = 2.708 (2) A?; 6, P21/n, a = 12.096 (4) A?, b = 24.474 (6) A?, c = 23.329 (5) A?, β = 100.73 (2)°, V = 6786 (3) A?3, Mo-Mo = 2.788 (1) A?.
