Synthetic routes to a series of novel oligomeric and polymeric platinum(II)-containing silylacetylenes have been developed. The CuI-catalyzed reaction of trans-[Pt(PEt3)2PhCl] with the alkynylsilane Ph2Si(C≡CH)2, in a basic medium, afforded the mononuclear trans-[Ph(Et3P)2PtC≡CSiPh2C≡CH] (1) and the dinuclear trans[Ph(Et3P)2PtC≡CSiPh2C≡CPt(PEt3)2Ph] (2). Complex 1 can be utilized as a key starting material for access to the triplatinum(II) system trans-[Ph(Et3P)2PtC≡CSiPh2C≡CPt(PBu3)2C≡CSiPh2C≡Pt(PEt3)2Ph] (3). Attempted oxidative coupling of 1 only led to the isolation of the triacetylenic species trans-[Ph(Et3P)2PtC≡CC≡CC≡CPt(PEt3)2Ph] (5), involving cleavage of Si-C(alkyne) bonds. Soluble and thermally stable platinum(II) poly-yne silane polymer trans-[-Pt(PBu3)2C≡CSiPh2C≡C-]n(4) was prepared in good yield by CuI-catalyzed polymerization of trans-[Pt(PBu3)2Cl2] and Ph2Si(C≡CH)2. The single-crystal X-ray structural analyses and DFT calculations were performed on 1, 2 and 5. We report the optical absorption and photoluminescence spectra of these new metal-based oligomeric and polymeric silylacetylenes and the results are compared with platinum(II) poly-ynes with purely acetylenic and (hetero)aromatic conjugated units.
|Number of pages||8|
|Journal||Journal of the Chemical Society. Dalton Transactions|
|Publication status||Published - 21 Dec 2002|
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