Synthesis, structures and properties of platinum(II) complexes of oligoacetylenic sulfides

摘要

A series of novel platinum(II) acetylide complexes incorporating sulfur-linked oligoalkynes have been prepared. The Cul-catalysed dehydrohalogenation reactions of the mono-protected dialkyne ligand HC (ident to) CSC (ident to) C(TIPS) (TIPS = Pr_3~iSi) with trans-[Pt(PBu_3)_2Cl_2], cis-[Pt(dppe)Cl_2] or cis-[Pt(Me_2bipy)Cl_2] (Me_2bipy = 4,4'-dimethyl-2,2'-bipyridine), in the presence of a base, readily produced trans-[Pt(PBu_3)_2{C (ident to) CSC (ident to) C(TIPS)}_2] 1, cis-[Pt(dppe){C (ident to) CSC (ident to) C(TIPS)}_2] 3 and cis[Pt(Me_2bipy) {C (ident to) CSC (ident to) C(TIPS)}_2] 7, respectively, in good yields. Similar synthetic procedures using a diacetylenic sulfide species HC (ident to) CSC (ident to) CC (ident to) CSC (ident to) C(TIPS) afforded trans-[Pt(PBu_3)_2{C (ident to) CSC (ident to) CC (ident to) CSC (ident to) C(TIPS)}_2] 2 and cis-[Pt(dppe){C (ident to) CSC (ident to) CC (ident to) CSC (ident to) C(TIPS)}_2] 4, both of which contiam eight triple-bond units within the molecular entity. Two new metallo-end-capped derivatives trans-[Ph(Et_3P)_2PtC (ident to) CSC (ident to) C-Pt(PEt_3)_2Ph] 5 and trans-[Pt(Et_3P)_2Ph-C (ident to) CSC (ident to) CC (ident to) CSC (ident to) C-Pt(PEt_3)_2Ph] 6 were also synthesized in moderate yields yb reactions of two equivalents of trans-[PtPh(Cl)(Pet_3)_2] and the diterminal acetylenic sulfides HC (ident to) CSC (ident to) CH and HC (ident to) CSC (ident to) CC (ident to) CSC (ident to) CH in a CuI/(Me_3Si)_2NH system. All of the compounds 1-7 have been characterized by IR, NMR (~1H, ~(13)C and ~(31)P) and UV/VS spectroscopies, luminescence measurements and mass spectrometry. the solid-state molecular structures of 5 and 7 have been established by X-ray crystallography.