om6b00860_si_002.cif (2.89 MB)
Reactions of Osmium Carbyne Complexes OsCl3(CR)(PPh3)2 (R = CHCPh2, CH2Ar) with Bromine and Hydrogen Peroxide
dataset
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 JiaThe
reactions of the trichloro carbyne complexes OsCl3(CR)(PPh3)2 (R = CHCPh2, 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(CCHCPh2)(PPh3)2 with Br2/H2O and H2O2/HCl produced OsBr3(CCHCPh2)(H2O)(PPh3) and OsCl3(CCClCPh2)(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.