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Reaction of Et_4NI, NaSCH_2CO_2Et and Mo(CO)_6 in CH_3CN affords a new dinuclearmolybdenum (O) complex, [Et_4N]_2[Mo_2(CO)_B(SCH_2CO_2Et)_2] (1). Electrochemistry and reactivityinvestigation indicate that 1 undergoes an interesting two-electron oxidation in a single step (-0.43 V)and a substitution of its carbonyls by coordinating solvents resulting in two kinds of Mo(I)-complexes, Mo_2(CO)_8(SCH_2CO_2Et)_2 and (Mo_2(CO)_6SCH_2CO_2Et)_2(CH_3CN)_2. vc=o and vmo-co havebeen assigned. The crystal and molecular structure has been determined from three-dimensionalX-ray data. 1 crystallized in the triclinic, space group Pl with a=10.362(1), b=10.391(1), c=10.815(2); a=91.64(2)°, β=100.07(2)°, γ=114.46(1)°, Z=1; R=4.8% for 2975 reflectionswith I>3σ(I). Nonbonding of Mo…Mo [3.939(1)] and the configuration of MoS_2Mo unit in1 are very different from those in related Mo(I)-product. These results confirm our previous speculationthat the two-electron character derives from creation or cleavage of a metal-metal single bondcoupled with structural rearrangement in a bridged bimetallic center.
Reaction of Et_4NI, NaSCH_2CO_2Et and Mo (CO) _6 in CH_3CN affords a new dinuclear molybdenum (O) complex, [Et_4N] _2 [Mo_2 (CO) _B (SCH_2CO_2Et) _2] (1). Electrochemistry and reactivity investigation that said 1 ises an interesting two-electron oxidation in a single step (-0.43 V) and a substitution of its carbonyls by coordinating solvents resulting in two kinds of Mo (I) -complexes, Mo_2 (CO) _8 (SCH_2CO_2Et) _2 and (Mo_2 (CO) _6SCH_2CO_2Et The crystal and molecular structure has been determined from three-dimensional X-ray data. 1 crystallized in the triclinic, space group Pl with a = 10.362 (1), a = 91.64 (2) °, β = 100.07 (2) °, γ = 114.46 (1) °, Z = 1; R = 4.8% for 2975 reflections with I > 3σ (I). Nonbonding of Mo ... Mo [3.939 (1)] and the configuration of MoS_2Mo unit in1 are very different from those of related Mo (I) -product. These results confirm our previous speculation of the two-electron character derives from creation or clea vage of a metal-metal single bondcoupled with structural rearrangement in a bridged bimetallic center.