Syntheses and structures of monoplatinum model complexes for diplatinum polyynediyl adducts LnPt(CC)zPtLn

The CuI-catalyzed reactions of trans-(Ph3P)2PtCl2 with HCCSiMe3 or HCCCCSiMe3 (greater than two equivalents, HNEt2), and trans-(p-tol)(Ph3P)2PtCl (4) or trans-(C6F5)(p-tol3P)2PtCl with HCCCCH, give trans-(Ph3P)2Pt(CCSiMe3)2 (2), trans-(Ph3P)2Pt(CCCCSiMe3)2 (3), trans-(p-tol)(Ph3P)2PtCCCCH (5), and trans-(C6F5)(p-tol3P)2PtCCCCH (7) in 74–81% yields. These compounds are characterized crystallographically, and their physical properties compared. A convenient three-step synthesis of 4 from (COD)PtCl2 is described.