Formation and structures of novel polynuclear complexes containing Mo–Mo or Mo–Co bonds with bridging SR or PR 2 group

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Four dimolybdenum complexes with bridging thiolato groups, (η 5-C 5H 5)(CO)Mo(μ-SR) 3Mo(CO) 3 ( 4; R=Me, Ph, Bn (benzyl), Tol), were formed from Mo(CO) 3(NCMe) 3 and [C 5H 4SR] −. The related complex (η 5-C 5H 5)(CO)Mo(μ-SR) 3Mo(CO)(SR) 2 ( 5; R=Ph) was obtained when additional [C 5H 4SR] − was used in the reaction. The molecular structures of 4 (R=Bn) and 5 were determined by X-ray crystallography. A Mo 2Co complex ( 6) was obtained from (η 5-C 5H 4 −Li +)(CO) 3MoCo(CO) 4 and Ph 2PCl. The structure, determined from X-ray diffraction data, reveals some unusual bridging arrangements.