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Tsutsumi K.,Nara Instituted of Science and Technology NAIST | Sakai H.,Nara Instituted of Science and Technology NAIST | Sakonaka K.,Nara Instituted of Science and Technology NAIST | Yabukami T.,Nara Instituted of Science and Technology NAIST | And 5 more authors.
European Journal of Inorganic Chemistry | Year: 2010

The reaction of pentadiynyl halides XCH2C≡CC≡CPh (1) with equimolar amounts of Pt(C2H4)(PPh3) 2 in C6D6 produced cis-(PPh3) 2PtX(η1-CH2C≡CC≡CPh) (cis-2) as a kinetic product. Complex cis-2 isomerized to trans-(PPh3) 2PtX(η:lCH2C≡CC≡CPh) (trans-2) or trans-(PPh3)2PtX[η1-C(C≡ CPh)=C=CH2] (trans-3) under some reaction conditions. In contrast to the reaction of Pt(C2H4)(PPh3)2, treatment of 1 with Pt(PPh3)4 generated, cationic platinacyclobutene [(PPh3J2Pt(η2-CH 2C(PPh3)=C(C=CPh)}]+Cl- (5) together with cis-2 and trans-2. Moreover, 2 equiv. of Pt(C2H 4)(PPh3)2 and 1 provided eta;1, η2-coordinated diplatinum complex cis-(PPh3) 2-PtCl[η1- CH2C≡C((PPh 3)2Pt(η2-C≡CPh)] (7) and/or metallacyclobutene diplatinum complex (PPh3)2Pt[η 2-CH2C[(PPh3)2PtCl}=C(C≡CPh)J (8). The coordination modes of these complexes depend, on the ratio of pentadiynyl halide, Pt, and PPh3, as well as temperature and the nature of the solvents. Protonolysis of metallacyclobutene complexes 5 and 8 with HCl gave [cis-(PPh3)2PtCl{η1- C(C≡CPh)=C(PPh3)CH3}]+Cl- (9) and [(PPh3)2Pt(η3-CH2{cis- (PPh3)2PtCl}CCH(C≡CPh)}]+Cl- (10). Single-crystal X-ray diffraction analysis of 12 showed η3- and η1-coordination structure. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheira.

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