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Citation: Yang Yu, Cai Tao, Wen Tingbin. Alkenylcarbyne Complexes Derived from the Reactions of OsXCl-(PPh3)3(X=H, Cl) with Propargyl Chloride and Phosphine Ligand-Controlled Transformation of Hydride-Carbyne to Carbene[J]. Chinese Journal of Organic Chemistry, ;2017, 37(1): 176-184. doi: 10.6023/cjoc201608013 shu

Alkenylcarbyne Complexes Derived from the Reactions of OsXCl-(PPh3)3(X=H, Cl) with Propargyl Chloride and Phosphine Ligand-Controlled Transformation of Hydride-Carbyne to Carbene

  • Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

  • Corresponding author: Wen Tingbin, chwtb@xmu.edu.cn
  • Received Date: 18 August 2016
    Revised Date: 4 September 2016

    Fund Project: the National Natural Science Foundation of China 21072161the National Basic Research Program of Chin 973 Program, 2012CB821600

Figures(5)

  • Reactions of the simple osmium precursors OsHCl (PPh3)3(1) or OsCl2(PPh3)3(2) with 3-chloro-3-methylbut-1-yne afforded OsHCl2(≡CCH=CMe2)(PPh3)2(3) or OsCl3(≡CCH=CMe2)(PPh3)2(4), respectively.Treatment of 3 with Ph2PC≡CPh led to the formation of the tris-diphenyl (phenylethynyl) phosphine alkenylcarbene complex OsCl2(=CHCH=CMe2)(Ph2PC≡CPh)3(5), while complex 4 underwent simple phosphine ligand substitution with Ph2PC≡CPh to give OsCl3(≡CCH=CMe2)(Ph2PC≡CPh)2(6).Presumably, upon the phosphine ligand substitution of PPh3 in 3 by Ph2PC≡CPh, the relatively electron-poor nature of the later decreased the electron density of the osmium center, and thus promoted the transformation of the hydride-carbyne to carbene via the 1, 2-shift of the hydride ligand from Os to the carbyne carbon, which was then further facilitated by the coordination of a third less bulky Ph2PC≡CPh ligand to the osmium center to give the stable 18e product 5.
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