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

Bai, Wei; Lee, Ka-Ho; Hung, Wai Yiu; H. Y. Sung, Herman; Williams, Ian D.; Lin, Zhenyang; Jia, Guochen

doi:10.1021/acs.organomet.6b00860.s001

om6b00860_si_001.pdf (1.12 MB)

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

journal contribution

posted on 2017-01-18, 17:34 authored by Wei Bai, Ka-Ho Lee, Wai Yiu Hung, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin, Guochen Jia

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.