Article: En route to diplatinum polyynediyl complexes trans,trans-(Ar)[([R.sub.3]P).sub.2]Pt[(C[equivalent to]C).sub.n]Pt[([PR.sub.3]).sub.2](Ar): untold tales, including end-group strategies *.(Report)

Abstract: Reactions of [{([C.sub.6][F.sub.5])Pt[S[(C[H.sub.2]C[H.sub.2]-).sub.2]]([mu]-Cl)}.sub.2] and [R.sub.3]P yield the bis(phosphine) species trans-([C.sub.6][F.sub.5])[([R.sub.3]P).sub.2]PtCl [R = Et (Pt'Cl), Ph, [(p-C[F.sub.3][C.sub.6][H.sub.4]).sub.3]P; 88-81%]. Additions of Pt'Cl and H[(C[equivalent to]C).sub.n]H (n = 1, 2; H[NEt.sub.2], 20 mol% CuI) give Pt'[C.sub.2]H (37%, plus Pt'I, 16%) and Pt'[C.sub.4]H (88%). Homocoupling of Pt'[C.sub.4]H under Hay conditions (O2, CuCl, TMEDA, acetone) gives Pt'[C.sub.8]Pt' (85%), but Pt'[C.sub.2]H affords only traces of Pt'[C.sub.4]Pt'. However, condensation of Pt'[C.sub.4]H and Pt'Cl (H[NEt.sub.2], 20 mol% CuI) yields ...

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