Abstract
The tetrahedral alkylgallium(I) compound Ga4R41 [R = C(SiMe3)3] dissociates in solution with the formation of the monomeric fragments GaR, which are isolobal to carbon monoxide and are able to replace CO ligands in transition metal carbonyl complexes. By the substitution of two CO groups, the treatment of Mn2(CO)10 and Fe3(CO)12 with 1 yielded the two novel transition metal gallium complexes Mn2(CO)8(μ-GaR)22 and Fe3(CO)9(μ-CO)(μ-GaR)23, neither of which is isostructural to the starting carbonyl compounds. The GaR ligands bridge both manganese atoms of 2 with all carbonyl groups in terminal positions, and two edges of the central Fe3 triangle of 3 are occupied by GaR, while the third one is bridged by carbon monoxide.

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