LAUSR

Abstract Reactions of trans-(C6F5)(p-tol3P)2Pt(Cl) (PtCl) and R2PhP (1.0 equiv; R = a/Me, b/p-t-BuC6H4, c/p-MeOC6H4, d/n-Pr; CH2Cl2/rt (a) or toluene/reflux (b-d)) give mainly trans-(C6F5)(R2PhP)(p-tol3P)Pt(Cl) (Pt′Cl-a-d, 89-29%) and some disubstitution products trans-(C6F5)(R2PhP)2Pt(Cl) (Pt″Cl-a-d, 4–13%). No substitution occurs with t-Bu2PhP. However, (cod)(C6F5)Pt(Cl) and t-Bu2PhP (2.7 equiv; toluene/reflux) react to give trans-(C6F5)(t-Bu2PhP)2Pt(Cl) (Pt″Cl-e, 64%), which upon treatment with p-tol3P (1.0 equiv, toluene/reflux) yields trans-(C6F5)(t-Bu2PhP)(p-tol3P)Pt(Cl) (Pt′Cl-e, 91%). Additions of excess butadiyne to Pt′Cl-a-d (CH2Cl2, cat. CuI, HNEt2) afford the butadiynyl complexes trans-(C6F5)(R2PhP)(p-tol3P)Pt(C≡C)2H (Pt′C4H-a-d, 36–77%), but Pt′Cl-e does not similarly react. Cross couplings of Pt′Cl-a-c and Pt′C4H-a-c (cat. CuI, HNEt2) give mixtures of diplatinum butadiynyl complexes in which the two unlike phosphine ligands scramble over all four positions (PtC4Pt, PtC4Pt′-a-c, PtC4Pt″-a-c, Pt′C4Pt′-a-c, Pt′C4Pt″-a-c, Pt″C4Pt″-b; TLC separable, 27-2% each). A modified coupling recipe is tested with Pt′Cl-b,d and Pt′C4H-b,d (t-BuOK, KPF6, cat. CuCl), and gives Pt′C4Pt′-b,d (21–76%) with only traces of scrambling. Crystal structures of Pt″Cl-e, Pt′C4H-a, Pt′C4Pt′-a-d, and PtC4Pt″-b are determined, and the endgroup/endgroup interactions analyzed. Low temperature NMR spectra do not reveal any dynamic processes.