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Chinese Journal of Organic Chemistry >

2013 , Vol. 33 >Issue 08: 1697 - 1708

DOI: https://doi.org/10.6023/cjoc201305046

Articles

Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes

  • An Ran ,
  • Li Ting ,
  • Wen Ting-Bin
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  • Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Received date: 2013-05-27

  Revised date: 2013-05-31

  Online published: 2013-06-04

Supported by

Project supported by the National Natural Science Foundation of China (No. 21072161), the National Basic Research Program of China (973 Program, No. 2012CB821600), the Program for Changjiang Scholars and the Innovative Research Team in University (PCSIRT).

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Abstract

Reactions of the dihydride complex OsH2Cl2(PCy3)2 (1) with HC≡CC(OH)Ph2 at room temperature or under heating condition produce the hydride hydroxycarbyne complex OsHCl2[≡CCH2C(OH)Ph2](PCy3)2 (2) and the hydride alkenylcarbyne complex OsHCl2(≡CCH=CPh2)(PCy3)2 (3), respectively. Treatment of 2 or 3 with HCl·Et2O affords the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PCy3)2 (4), which can be conveniently synthesized by the one pot reaction of 1 with HC≡CC(OH)Ph2 in the presence of HCl·Et2O. Complex 4 can be alternatively prepared from the phosphine ligand substitution of the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PPh3)2 (5) with PCy3, from which the mono-substituted intermediate OsCl3(≡CCH=CPh2)(PCy3)(PPh3) (6) can be isolated. Complex 4 undergoes ligand substitution reactions with water and pyridine leading to the formation of the aqua and pyridine-coordinate mono phosphine carbyne complexes OsCl3(≡CCH=CPh2)(PCy3)(S) (S=H2O, 7; S=Py, 8). In addition, complex 4 reacts with NaOEt at room temperature to produce the alkenylcarbene complex OsCl2(=CHCH=CPh2)(PCy3)2 (9), which is unstable in solution and evolves into the thermally more stable hydride carbyne complex 3. In contrast, the reaction of 4 with EtOH can only take place at elevated temperature to give the hydride carbyne 3.

Key words： osmium; carbyne; carbene; terminal alkyne; hydride complex

Cite this article

An Ran , Li Ting , Wen Ting-Bin . Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes[J]. Chinese Journal of Organic Chemistry, 2013 , 33(08) : 1697 -1708 . DOI: 10.6023/cjoc201305046

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