Formation of clusters by oxidative addition of organic and inorganic disulfides. Molecular structures of (Me(CN)2(CO)6Mo2(μ-SPh)2 and Mo2Fe7S8(CO)22

Abstract Reactions of the disulfides Ph 2 S 2 and (CO) 6 Fe 2 s 2 with (MeCN) 3 Mo(CO) 3 (I) leading to the splitting of SS bonds have been studied. Binuclear (MeCN) 2 (CO) 6 Mo 2 (μ-SPh) 2 (II) is obtained from the reaction of I with Ph 2 S 2 . The X-ray diffraction data for II (space group P 2 1 , a 9.262(4), b 9.343(10), c 15.494(6), β 105.85(3), Z = 2, R = 0.037) show the MoMo bond of length (2.982(1) A), to be supported by thiolate bridges (MoS 2.468(1) A). Interaction of I with the ferrosulfide dimer breaks the SS and FeFe bonds to give an antiferromagnetic nonanuclear cluster Mo 2 Fe 7 S 8 (CO) 22 (III) (μ eff 2.61(298 K) − 1.92(78 K) BM). An X-ray diffraction study (space group P 1 , a 13.003(2), b 14.278(1), c 16.019(2) A, α = 109.555(8), β 97.187(10), γ 113.006(7)°, Z = 2, R = 0.045) has revealed that molecule III consists of two fragments (CO) 9 Fe 3 (S) 4 Mo(CO) 2 (MoFe 2.750(2) A, FeS 2.260(3) A, MoS 2.406(3) A) linked via the Fe atom (MoFe 2.900(2) A, FeS 2.242(3) and 2.529(3) A), but without FeFe bonds.