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Effects of substituents on the formation of rhenium carbyne and eta(2)-vinyl complexes from the reactions of ReH5(PMe2Ph)(3) with terminal alkynes

Authors He, Guomei HKUST affiliated (currently or previously).
Fan, Ting HKUST affiliated (currently or previously)
Chen, Jiangxi 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 2013
Source New Journal of Chemistry , v. 37, (6), June 2013, p. 1823-1832
Summary The reactions of the rhenium polyhydride complex ReH5(PMe2Ph)(3) with HC CAr (Ar = p-C6H4CF3, o-C6H4CF3, o-C6H4Me and o-C6H4Br) have been carried out. Treatment of ReH5(PMe2Ph)(3) with HC C(p-C6H4CF3) in the presence of two equiv. of HCl produces a mixture of the carbyne complex Re( CCH2(p-C6H4CF3))Cl-2(PMe2Ph)(3) and the eta(2)-vinyl complex Re(eta(2)-CH2C(p-C6H4CF3))Cl-2(PMe2Ph)(3). Treatment of ReH5(PMe2Ph)(3) with HC CAr (Ar = o-C6H4CF3, o-C6H4Me, o-C6H4Br) in the presence of two equiv. of HCl produces only the carbyne complexes Re( CCH2Ar)Cl-2(PMe2Ph)(3). The mechanism of the reactions of ReH5(PMe2Ph)(3) with HC CR has also been studied with the aid of DFT calculations, which suggests that the reactions are kinetically controlled and the pathways leading to the carbyne and eta(2)-vinyl complexes are influenced by the steric and electronic effects of the substituents of the alkynes.
ISSN 1144-0546
Language English
Format Article
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