American Chemical Society
om6b00860_si_002.cif (2.89 MB)

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

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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.