Interaction of Triosmium Complexes with Hydrogen Chloride: A Model for Fine-Tuning Regioselective Protonation in Metal Clusters
作者： Min-Ling Chung , Fang-Yuan Lee , Li-Chun Lin , Chi-Jung Su , Min-Yen Chen
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摘要: The reaction of Os3(CO)10(CNR)(NCMe) (1) with HCl was studied and this system found to be a good model for observing the fine-tuning site-selective protonation in metal complexes. Three products including protonated species [(e-H)Os3(CO)10(CNR)(NCMe)]+Cl− (2), bridging aminocarbyne complex (µ-Cl)Os3(CO)10(µ2-C = NHR) (3), hydrido derivative (e-H)Os3Cl(CO)10(CNR) (4) were obtained reaction. site protonation, either on Os center or nitrogen atom coordinated isocyanide, tuned sensitive manner by nature isocyanides, polarity solvents, strengths acids, leading different product distributions. more electron withdrawing isocyanides (CNCH2Ph, CNPh) favor formation 3. In nonpolar solvent like cyclohexane afforded 3 as main product. Furthermore, 2 converted (e-H)Os3(CO)10(e2-CONHR) (5) upon hydrolysis, which isocyanide transformed carboxamido group. This verified obtaining deuterated (e-H)Os3(CO)10(e2-CONDPr) when [(e-H)Os3(CO)10(CNPr)(NCMe)]+Cl− (2a) treated D2O THF. molecular structures (µ2-Cl)Os3(CO)10(µ2-C NHCH2Ph) (3b) (e-H)Os3Cl(CO)10(CNPr) (4a) determined X-ray diffraction analyses. Complex 3b contains both chloride groups, whereas 4a terminal chloride, hydride.
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