Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)2Os3(CO)10

Abstract

A reaction has been found and investigated that demonstrates the potential for coordination, activation, and transformation of three organic molecules, namely, two dichloromethane molecules and one amine molecule, in the coordination sphere of the [(µ‐H)Os3(CO)10]– carbonylate anion, which is formed in situ from the deprotonation of [(µ‐H)2Os3(CO)10]. This reaction is very intricate and comprises such steps as the nucleophilic substitution of chloride ions by cluster carbonylate anions in the halocarbons, C–H, C–N, and C–Cl bond cleavage, and C–C and C–N bond formation under unusually mild conditions for such reactions leading to the formation of the CH=CH2‐ or CH=CHNR2‐bearing complexes [(µ‐Cl)Os3(µ2‐σ,π‐CH=CH2)(CO)10] and [(µ‐H)Os3(µ‐CH=CHNR2)(CO)10]. The reaction is sensitive to the nature of the halogen in the halocarbon. When bromine or iodine was used in place of chlorine in the halohydrocarbons, [(µ‐H)Os3(µ‐X)(CO)10] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the SN2 mechanism by SN2Hal.