Syntheses, Structures, and Electronic and Photophysical Properties of Unsymmetrically Substituted Butadiynediyl and Hexatriynediyl Complexes Derived from (C6F5)(R3P)2Pt, (p-tol)(R3P)2Pt, and (Ph3P)Au End-Groups

The CuCl-catalyzed reaction of butadiynyl complex trans-(C6F5)(Et3P)2Pt(C≡C)2H (6) and trans-(p-tol)(Et3P)2PtCl (7) in HNEt2 affords trans,trans-(C6F5)(Et3P)2Pt(C≡C)2Pt(PEt3)2(p-tol) (8; 62%), but similar reactions of p-tol3P-substituted coupling partners, or of 6 and trans-(p-tol)(p-tol3P)2PtCl (4), are not successful. However, 6 and 4 react under modified conditions (t-BuOK, KPF6, cat. CuCl, THF/methanol) to give trans,trans-(C6F5)(Et3P)2Pt(C≡C)2Pt(Pp-tol3)2(p-tol) (9; 91%). The hexatriynyl complexes trans-(C6F5)(R3P)2Pt(C≡C)3H (R = p-tol, Et) are treated with 4 and 7, respectively, under the original or modified conditions. Workups give trans,trans-(C6F5)(R3P)2Pt(C≡C)3Pt(PR3)2(p-tol) (R = p-tol, 12, 40−63%; Et, 17, 59%). The reaction of 6 and ClAu(PPh3) and KN(SiMe3)2 affords trans-(C6F5)(Et3P)2Pt(C≡C)2Au(PPh3) (18, 97%). The CuCl-catalyzed reaction of (η5-C5H5)W(CO)3(C≡C)2H and trans-(C6F5)(Et3P)2PtCl in HNEt2 generates trans-(C6F5)(Et3P)2Pt(C≡C)2W(CO)3(η5-C5H5). The crystal structures of 8, 9, 17, an...