Please use this identifier to cite or link to this item:

Rearrangement of Metallabenzynes to Chlorocyclopentadienyl Complexes

Authors Chen, Jiangxi HKUST affiliated (currently or previously)
Lee, Kaho HKUST affiliated (currently or previously)
Wen, Tingbin HKUST affiliated (currently or previously)
Gao, Feng HKUST affiliated (currently or previously).
Sung, Herman Ho Yung HKUST affiliated (currently or previously)
Williams, Ian Duncan View this author's profile
Lin, Zhenyang View this author's profile
Jia, Guochen View this author's profile
Issue Date 2015
Source Organometallics , v. 34, (5), March 2015, p. 890-896
Summary Treatment of the osmabenzyne complex Os{=C-C(SiMe3)-C(CH3)-C(SiMe3)-CH-}Cl2(PPh3)(2) with Mo(CO)(6) in refluxing benzene produced the eta(5)-chlorocyclopentadienyl complex Os{eta(5)-C5HCl(CH3)(SiMe3)(2)}Cl(CO)(PPh3) and Mo(CO)(5)(PPh3). A computational study suggests that the chlorocyclopentadienyl complex is most likely produced via the carbene intermediate Os{-C(C(SiMe3)-C(CH3)-C(SiMe3)-CH-)}Cl-2(CO)(PPh3) formed by a migratory insertion reaction of the osmabenzyne complex Os{=C-C(SiMe3)-C(CH3)-C(SiMe3)-CH}Cl-2(CO)(PPh3). DFT calculations show that the relative thermal stability of metallabenzynes Os(=C-CH-CHCH-CH)Cl-2(L)(2) and the corresponding isomeric carbene complexes Os{-C(-CH-CHCH-CH-)}Cl2(L)2 as well as the chlorocyclopentadienyl complexes Os(eta(5)-C5ClH4)Cl(L)(2) (L = CO, phosphine, pyridine, amine) is strongly dependent on ligand L.
ISSN 0276-7333
Language English
Format Article
Access View full-text via DOI
View full-text via Web of Science
View full-text via Scopus