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[Display omitted] Reactions of the electron defficient triosmium [Os 3 (CO) 9 (μ 3 -η1,κ1-C 9 H 6 N)(μ-H)] with Ph 3 EH (E = Si, Ge, Sn) have been investigated. The reactions of quinoline-capped triosmium cluster [Os 3 (CO) 9 (μ 3 -η1,κ1-C 9 H 6 N)(μ-H)] (1) with Ph 3 EH (E = Si, Ge, Sn) have been investigated. Cluster 1 reacts with Ph 3 EH in refluxing benzene to afford [Os 3 (CO) 9 (EPh 3)(μ-η1,κ1-C 9 H 6 N)(µ-H) 2 ] (2a , E = Si; 2b , E = Ge; 2c , E = Sn) and [Os 3 (CO) 8 (EPh 3)(μ 3 -η1,κ1-C 9 H 6 N)(µ-H) 2 ] (3a , E = Si; 3b , E = Ge; 3c , E = Sn). Control experiments confirm that 2 is a precursor of 3. Cluster 2 is formed via oxidative-addition of E–H bond to 1 whose decarbonylation leads to the formation of 3. The molecular structures of all the new clusters (except 3c) have been determined by X-ray crystallography. Both 2 and 3 exist as a pair of isomers in solution, and their fluxionality in solution has been probed by VT NMR experiments. [ABSTRACT FROM AUTHOR]