Abstract
The reactions of the rhenium polyhydride complex ReH5(PMe2Ph)3 with HCCAr (Ar = p-C6H4CF3, o-C6H4CF3, o-C6H4Me and o-C6H4Br) have been carried out. Treatment of ReH5(PMe2Ph)3 with HCC(p-C6H4CF3) in the presence of two equiv. of HCl produces a mixture of the carbyne complex Re(CCH2(p-C6H4CF3))Cl2(PMe2Ph)3 and the η2-vinyl complex Re(η2-CH2C(p-C6H4CF3))Cl2(PMe2Ph)3. Treatment of ReH5(PMe2Ph)3 with HCCAr (Ar = o-C6H4CF3, o-C6H4Me, o-C6H4Br) in the presence of two equiv. of HCl produces only the carbyne complexes Re(CCH2Ar)Cl2(PMe2Ph)3. The mechanism of the reactions of ReH5(PMe2Ph)3 with HCCR 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 η2-vinyl complexes are influenced by the steric and electronic effects of the substituents of the alkynes.
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