Convenient route to an electron-deficient Tetraosmium(I) Carboxylate chain

•Convenient synthesis of an electron-deficient tetraosmium chain.•Build-up of a tetraosmium chain from a diosmium precursor.•First example of a tetraosmium(I) carboxylate chain with an unsupported Os–Os bond.•Computational studies of a simplified structure Os4(CO)8(μ-OOCMe)4(PMe3)2.

Refluxing the dinuclear complex [Os2(CO)6(μ-OOCtBu)2] in acetonitrile affords the substituted derivative [Os2(CO)4(μ-OOCtBu)2(NCMe)2]. Their reaction with PPh3 in a 2:1 (Os:PPh3) ratio represents a convenient route to the 64-electron, tetraosmium chain [Os4(CO)8(μ-OOCtBu)4(PPh3)2].

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