Isolation and characterization of thiolato complexes of [CpCr(SBz)]2S, isomeric trans [CpMo(CO)(SBz)]2 and [CpMo(SBz)2]2 (Cp = (η5-C5H5), Bz = PhCH2) from the reactivity of bibenzyl disulfide towards [CpM(CO)3]2 (M = Cr, Mo)

Abstract The reactions of [CpM(CO) 3 ] 2 (M = Cr ( 1 ), Mo ( 3 )) with Bz 2 S 2 have been investigated. 1 underwent a facile reaction at ambient temperature which led to the isolation of [CpCr(CO) 2 ]S ( 5 ), [CpCr(CO) 2 (SBz)] 2 ( 6 ) and [CpCr(SBz)] 2 S ( 7 ) in 28.8, 42.6 and 11.8% yield, respectively. A similar reaction at 110 °C with its congener, [CpCr(CO) 2 ] 2 (Cr Cr) ( 2 ) yielded only thermolytic products of 5 (40.3%) and Cp 4 Cr 4 S 4 ( 8 ) (10.6%). With the Mo analogue 3 , only the decarbonylated [CpMo(CO) 2 ] 2 (Mo Mo) ( 4 ) reacts at 70 °C to give an isomeric pair of trans syn and anti [CpMo(CO)(SBz)] 2 ( 9a & 9b ), [CpMo(SBz)(S)] 2 ( 10 ) and [CpMo(CO)(SBz)] 2 S ( 11 ) in 43.3, 34.1, 5.5 and 3.1% yield, respectively. A totally decarbonylated new complex of [CpMo(SBz) 2 ] 2 ( 12 ) was obtained in 33.2% yield from the co-thermolysis of Bz 2 S 2 with 9a at 110 °C. All products were fully characterized with NMR and IR spectroscopy and C, H analysis. The molecular structures of 7 , 9b and 12 have been elucidated by single crystal X-ray diffraction. Plausible mechanistic pathways leading to the formation of 7 , 9 and 12 were discussed.