Structures of three novel polynuclear oxo- and sulfidomolybdenum complexes containing the hydrotris(3,5-dimethyl-1-pyrazolyl)borate ligand

The complexes [{HB(Me₂pz)₃}MoS(μ-S)₂MoO(μ-OH)]₂ (1), [{HB(Me₂pz)₃}MoO]₂(μ-O)(μ-S₂) (2), and {HB(Me₂pz)₃}MoS(μ-S)₂MoS(S₂CNEt₂) (3) have been isolated and characterized by X-ray crystallography. 1.3C₂H₄C1₂ crystallizes in the triclinic space group C̅1 with a = 18.421 (3) Å,b = 10.547 (3) Å, c = 15.575 (4) Å, α = 90.07 (2)°, β = 104.76 (2)°, ³ = 90.53 (2)°, and Z = 2. Each linear tetranuclear complex possesses 1 symmetry. 2.½C₆H₆ crystallizes in monoclinic space group P2₁/n with a = 15.126 (1) Å, b = 14.364 (2) Å, c = 20.145 (2) Å, β = 105.835 (7)°, and Z = 4. Complex 2 contains a rare mode of cis end-on disulfide bridge in which each molybdenum is coordinated to a different sulfur atom of the S₂^2- ligand. 3.²/₃CH₂Cl₂crystallizes in the triclinic space group P̅1 with a = 12.103 (3) Å, b = 16.107 (4) Å,c = 26.404 (7) Å, α = 79.82 (2)°, β = 82.00 (2)°, γ = 85.51 (2)°, and Z = 6. This binuclear complex contains both a six-coordinate molybdenum atom with an N₃S₃coordination sphere and a five-coordinate molybdenum atom having only sulfur donor ligands. There are five different types of molybdenum-sulfur bonds in 3.