Structure of [Et 4N] 2[Mo 2(CO) 8(μ-SPh) 2] and structural chemistry of dinuclear molybdenum(0,I) carbonyl complexes containing thiolato bridges

Abstract

The crystal and molecular structure of the dinuclear molybdenum(O) carbonyl complex containing thiophenyl bridges, [Et 4N] 2[Mo 2(CO) 8(μ-SPh) 2] ( 1) was determined from three-dimensional X-ray data. 1 crystallizes in the triclinic, space group P 1 with a=9.841(2), b=9.921(4), c=11.848(2) Å; α= 81.80(3)°, β=85.64(2)°, γ=82.06(3)°; V=1038.9- (6) Å 3; Z=1; R=0.068 for 3228 independent reflections with I⩾3σ( I). A planar MoS 2Mo bimetallic framework with a large Mo…Mo distance of 4.069- (1)·Å which obviously indicates the absence of MoMo bonding was contained in the centrosymmetric structure of the anion of 1, [Mo 2(CO) 8(μ- SPh) 2] 2−. Studying the structure of 1 and comparing 1 with [Et 4N] 2[Mo 2(CO) 8(μ-SCH 2CO 2Et) 2] ( 2), Mo 2(CO) 8(μ-SCH 2CO 2Et) 2 ( 3), Mo 2(CO) 6(μ-SCH 2- CO 2Et) 2(MeCN) 2 ( 4) and Mo 2(CO) 6(μ-SPh) 2(Me- CN) 2 ( 5), the structural chemistry of dinuclear molybdenum(O,I) carbonyl complexes containing thiolato bridges and the relevance to their properties and electrochemistry were discussed.