Synthese und Reaktionsverhalten von Platin(II) und Kupfer(I) Koordinationspolymeren; die Festkörperstruktur von {trans-(Ph3P)2Pt[(η2-CCPh)CuBr]2}n und trans-(Ph3P)2Pt[(η2-CCPh)CuNO3]2

The title complex {trans-(Ph3P)2Pt[(η2-CCPh)CuX]2}n (3a, X=Cl; 3b, X=Br) can be prepared by treatment of trans-(Ph3P)2Pt(CCPh)2 (1) with two equivalents of [CuX] (2a, X=Cl; 2b, X=Br) in quantitative yield. The reaction chemistry of 3b towards organic chelating molecules is reported. Treatment of 3b with, for example, 2,2′-bipy (4) produces the chelated copper(I) species [(bipy)CuBr]2 (6) along with 1. However, if 3b is reacted with the silver(I) salt [AgNO3] (5a) then trimetallic trans-(Ph3P)2Pt [(η2-CCPh)CuNO3]2 (7) is formed in which each phenylethynyl ligand is η2-coordinated to a copper(I) nitrate unit. This complex is also obtained, when 1 is reacted with two equivalents of [Cu(NCMe)4]NO3 (5b). The solid-state structures of 3b and 7 are reported. Polymeric 3b crystallises in the triclinic space group with cell parameters a=11.5958(3) Å, b=13.3491(3) Å, c=15.4875(4) Å, α=81.755(1)°, β=87.324(1)°, γ=85.472(1)°, V=2363.66(10) Å3, Z=2 and ρ=1.818 g mol−1. Complex 7: monoclinic space group P2/n with a=9.8971(1), b=14.2324(3), c=16.6957(2) Å, β=105.478(1)°, V=2266.46(6) Å3, Z=2 and ρ=1.719 g mol−1. In 3b a linear polymeric structure is adopted. 3 contains two crystallographic independent trans-Pt(CCPh)2 units which are linked by 4-membered Cu2(μ-Br)2 cycles at which the respective PhCC units are η2-coordinated to the copper(I) ions. In 7 each of the two PhCC entities is π-bound to a mononuclear CuNO3 moiety of which the NO3 ligand is chelate-bound to copper(I).