Molybdenum–tin and molybdenum–copper complexes derived from the molybdenum tricarbonyl anions, LMo(CO)3− (where L = HBpz3 or HBpz″3; pz = pyrazolyl, N2C3H3; and pz″ = 3,5-dimethylpyrazolyl, N2C5H7)

Abstract

The pyrazolylborate molybdenum tricarbonyl anions, (HBpz3)Mo(CO)3− and (HBpz″3)Mo(CO)3−, have been utilized to prepare a number of heteronuclear bimetallic species containing Mo—Sn and Mo—Cu bonds. Crystals of [hydrotris(1-pyrazolyl)borato-N,N,N](triphenylstannyl)tricarbonylmolybdenum are monoclinic, a = 17.570(2), b = 14.077(2), c = 12.180(1) Å, β = 96.985(8)°, Z = 4, space group P21/n, those of [hydrotris(1-3,5-dimethylpyrazolyl)borato-N,N,N](chlorodimethylstannyl)tricarbonylmolybdenum are monoclinic, a = 11.044(3), b = 12.061(2), c = 20.218(4) Å, β = 100.43(1)°, Z = 4, space group P21/c, and those of [hydrotris(1-pyrazolyl)borato-N,N,N]tricarbonylmolybdenum(N,N,N′,N′-tetramethylethylenediamine)copper dichloromethane solvate are orthorhombic, a = 19.027(2), b = 16.995(2), c = 16.136(2) Å, Z = 8, space group Pbca. The structures were solved by conventional heavy atom methods and refined by full-matrix least-squares procedures to R = 0.044, 0.042, and 0.059 for 2084, 2502, and 1891 reflections, respectively. The two tin structures have a 3:3:1 capped octahedral structure with Mo—Sn bonds of 2.864(1) and 2.823(1) Å. The copper complex has a 3:4 piano stool arrangement of ligands about Mo with a Mo—Cu bond of 2.639(2) Å, two semibridging carbonyl ligands, and one terminal carbonyl ligand.