Linear Trinuclear Pt···Mo−Mo Complexes [Mo<sub>2</sub>PtX<sub>2</sub>(pyphos)<sub>2</sub>(O<sub>2</sub>CR)<sub>2</sub>]<sub>2</sub> (X = Cl, Br, I; R = CH<sub>3</sub>, C(CH<sub>3</sub>)<sub>3</sub>; pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo<sub>2</sub> Moiety and the Platinum Atom
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An example of a direct axial interaction of a platinum(II) atom with a Mo2 core through a uniquely designed tridentate ligand 6-(diphenylphosphino)-2-pyridonate (abbreviated as pyphos) is described. Treatment of PtX2(pyphosH)2 (2a, X = Cl; 2b, X = Br; 2c, X = I) with a 1:1 mixture of Mo2(O2CCH3)4 and [Mo2(O2CCH3)2(NCCH3)6]2+ (3a) in dichloromethane afforded the linear trinuclear complexes [Mo2PtX2(pyphos)2(O2CCH3)2]2 (4a, X = Cl; 4b, X = Br; 4c, X = I). The reaction of [Mo2(O2CCMe3)2(NCCH3)4]2+ (3b) with 2a−c in dichloromethane afforded the corresponding pivalato complexes [Mo2PtX2(pyphos)2(O2CCMe3)2]2 (5a, X = Cl; 5b, X = Br; 5c, X = I), whose bonding nature is discussed on the basis of the data from Raman and electronic spectra as well as cyclic voltammograms. The linear trinuclear structures in 4b and 5a−c were confirmed by NMR studies and X-ray analyses: 4b, monoclinic, space group C2/c, a = 34.733(4) Å, b = 17.81(1) Å, c = 22.530(5) Å, β = 124.444(8)°, V = 11498(5) Å3, Z = 8, R = 0.060 for 8659 reflections with I > 3σ(I) and 588 parameters; 5a, triclinic, space group P1̄, a = 13.541(3) Å, b = 17.029(3) Å, c = 12.896(3) Å, α = 101.20(2)°, β = 117.00(1)°, γ = 85.47(2)°, V = 2599(1) Å3, Z = 2, R = 0.050 for 8148 reflections with I > 3σ(I) and 604 parameters; 5b, triclinic, space group P1̄, a = 12.211(2) Å, b = 20.859(3) Å, c = 10.478(2) Å, α = 98.88(1)°, β = 112.55(2)°, γ = 84.56(1)°, V = 2433.3(8) Å3, Z = 2, R = 0.042 for 8935 reflections with I > 3σ(I) and 560 parameters; 5c, monoclinic, space group P21/n, a = 13.359(4) Å, b = 19.686(3) Å, c = 20.392(4) Å, β = 107.92(2)°, V = 5101(2) Å3, Z = 4, R = 0.039 for 8432 reflections with I > 3σ(I) and 560 parameters.
