The interaction of the triangulo-trirhenium cluster alkyls, Re₃Cl₃(CH₂SiMe₃)₆ and Re₃Me₉, With carboxylic acids, β-diketones, and 1,3-diphenyltriazene leads to partial or complete loss of tetramethylsilane or methane from the end alkyl groups, respectively, and the formation of rhenium(III) complexes that may be either monomeric, i.e. triangulo-trirhenium, Re₃, or dimeric in which two such units are linked together by carboxylate bridges to give Re₆ species.

Examples of monomeric complexes are the benzoate, Re₃Cl₃(CO₂Ph)₆, β-diketonates, Re₃Me₆(β-dik)₃, and the diphenyltriazenide, Re₃Cl₃(CH₂SiMe₃)₃(PhN₃Ph)₃.

The dimeric complexes are carboxylates such as Re₆(µ-Cl₆)(CH₂SiMe₃)₆(µ-CO₂Me)₆ and Re₆(µ-Me₆)Me₆(µ-CO₂Me)₆, in which the Cl or Me bridges between rhenium atoms in each Re₃ triangle are retained.

I.r. and ¹H n.m.r. spectra are reported and likely structures for the complexes suggested.