A PMR study of the reaction of trinuclear osmium clusters HOs3(X)(CO)10 with organic acids

H–D exchange in metal carbene complexes: Structure of cluster (μ-H)(μ-OCD3)Os3(CO)9{:C(CD3)NC2H8O}

“…Significantly, that some bases are highly reactive toward the cluster bridging ligands. So it is known that three electron ligands in osmium cluster carbonyl complexes can be easily substituted by various nucleophiles [11,12] and this fact we observed in our investigation. The reaction study showed the hydrogen-deuterium exchange in the methyl group of 1.…”

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H4Os4(CO)12] and [HOs3(CO)10Y] (Y = OH, OR, Cl, Br, I, O2CR, SCN) Clusters from [Os3(CO)12]

“…(ii) From [HOs 3 (CO) 10 (OH)]. We further reinvestigated the reactivity of [HOs 3 (CO) 10 (OH)] with CH 3 CO 2 H. The reaction is very slow at room temperature, as previously reported . However, by heating an excess of CH 3 CO 2 H in heptane under reflux, [HOs 3 (CO) 10 (O 2 CCH 3 )] is obtained in 90% yield after 5 h (total yield starting from [Os 3 (CO) 12 ] 82%; Table ).…”

“…Derivatives of the type [HOs 3 (CO) 10 (O 2 CR)] (R = Me, CF 3 , Et, Ph) were first prepared in high yields (90%; total yields starting from [Os 3 (CO) 12 ] 40%) by reaction of [Os 3 (CO) 10 (cyclohexa-1,3-diene)] with an excess of RCO 2 H in refluxing cyclohexane . Addition of excess CF 3 CO 2 H to a solution of either [HOs 3 (CO) 10 (OCHCH 2 )] or [HOs 3 (CO) 10 (NCHNMe 2 )] also gives [HOs 3 (CO) 10 (O 2 CCF 3 )] in almost quantitative yield (total yields starting from [Os 3 (CO) 12 ] ∼55%). , Moreover, it was reported that dissolution of [HOs 3 (CO) 10 (OH)] in CF 3 CO 2 H at room temperature affords [HOs 3 (CO) 10 (O 2 CCF 3 )] quantitatively whereas the related reaction with CH 3 CO 2 H is quite slow (50% conversion after 46 days at room temperature); however, when this synthesis was reported, it had the inconvenience that [HOs 3 (CO) 10 (OH)] could be prepared only in low yields from [Os 3 (CO) 12 ] (9−27%). , …”