Reactions of Osmium Carbyne Complexes OsCl3(CR)(PPh3)2 (R = CHCPh2, CH2Ar) with Bromine and Hydrogen Peroxide

Jia, Guochen

Reactions of Osmium Carbyne Complexes OsCl₃(CR)(PPh₃)₂ (R = CHCPh₂, CH₂Ar) with Bromine and Hydrogen Peroxide

Posted on 2017-01-18 - 17:34

The reactions of the trichloro carbyne complexes OsCl₃(CR)(PPh₃)₂ (R = CHCPh₂, CH₂Ar) with bromine and hydrogen peroxide were studied. Unlike monochloro carbyne complexes OsCl(CAr)(CO)(PPh₃)₂, the trichloro complexes OsCl₃(CR)(PPh₃)₂ do not undergo oxidation reactions at the metal center or the metal–carbyne bond. Treatment of OsCl₃(CCHCPh₂)(PPh₃)₂ with Br₂/H₂O and H₂O₂/HCl produced OsBr₃(CCHCPh₂)(H₂O)(PPh₃) and OsCl₃(CCClCPh₂)(PPh₃)₂, respectively. Reactions of OsCl₃(CCH₂-C₆H₄-p-R)(PPh₃)₂ (R = H, CMe₃) with H₂O₂/HCl or H₂O₂ gave OsCl₃{CC(O)-C₆H₄-p-R}(PPh₃)₂. Computational studies suggest that the difference in the reactivity of OsCl(CAr)(CO)(PPh₃)₂ and OsCl₃(CR)(PPh₃)₂ is mainly of thermodynamic origin.

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Bai, Wei; Lee, Ka-Ho; Hung, Wai Yiu; H. Y. Sung, Herman; Williams, Ian D.; Lin, Zhenyang; et al. (2017). Reactions of Osmium Carbyne Complexes OsCl₃(CR)(PPh₃)₂ (R = CHCPh₂, CH₂Ar) with Bromine and Hydrogen Peroxide. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.6b00860

https://doi.org/10.1021/acs.organomet.6b00860

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