One-pot syntheses of alkenyl-phosphomo complexes of ruthenium(II), rhodium(III) and iridium(III) bearing p-cymene or pentamethylcyclopentadienyl groups

摘要

Reaction of [(p-cymene)RuCl2(PPh3)] (1) or [Cp*MCl2(PPh3)] (Cp* = C5Me5) (3a: M = Rh; 4a: M = Ir) with 1-alkynes and PPh3 were carried out in the presence of KPF6, generating the corresponding alkenyl-phosphonio complexes, [(p-cymene)RuCl(PPh3)tCH=CR(PPh3)}](PF6) (2a: R = Ph; 2b: R =p-tolyl) or [Cp*MCl(PPh3){CH=CPh(PPh3)}](PF6) (5: M = Rh; 6: M = Ir). Similar reactions of complexes [Cp*RhCl2(L-1)] (3a: L-1 = PPh3; 3c: L-1 = P(OMe)(3)) with L-2 (L2 = PPh3, PMePh2, P(OMe)(3)) gave [Cp*RhCl(L-1)(L-2)](PF6) (7bb: L-1 = L-2 = PMePh2; 7ca: L-1 = P(OMe)(3), L-2 = PPh3; 7cc: L-1 = L-2 = P(OMe)(3)). Alkenyl-phosphonio complex 5 was treated with P(OMe)(3) or 2,6-xylyl isocyanide, affording [Cp*RhCI(L){CH=CPh(PPh3)}] (PF6) (8a: L = P(OMe)(3); 8b: L = 2,6-xylNC). X-ray structural analyses of 2a, 6 and 8a revealed that the phosphonium moiety bonded to the C-p atom of the alkenyl group are E configuration. (c) 2007 Elsevier B.V. All rights reserved.