Iridium and rhodium complexes containing dichalcogenoimidodiphosphinato ligands

摘要

Treatment of [MCl(CO)(PPh3)(2)] with K[N(R(2)PQ)(2)] afforded [M{N(Ph(2)PQ)(2)}(CO)(PPh3)] (M = Ir, Rh; Q = S, Se). The IR C=O stretching frequencies for [M(CO)(PPh3){N(Ph(2)PQ)(2)]} were found to decrease in the order S > Se. Treatment of [M(COD)Cl](2) with K[N(Ph(2)PQ)(2)] afforded [M(COD){N(Ph(2)PQ)(2)}] (COD = 1,5-cyclooctadiene; M = Ir, Rh; Q = S, Se). Treatment of [Ir(ol)(2)Cl] with K[N(Pr(2)(i)pQ)(2)] afforded [Ir(ol)(2){N(Pr(2)(i)PQ)(2)}](2) (ol = cyclooctene COE, C2H4; Q = S, Se). Oxidative addition of [Ir(CO)(PPh3)K[N((Ph2S)-S-i)(2)}] and [Ir(COD){N(Ph2PS)(2)}] with HCl afforded [Ir(H)(Cl)(CO)(PPh3){N(Ph2PS)(2)}] and trans-[Ir(H)(Cl)(COD){N(Ph2PS)(2)}], respectively. Oxidative addition of [Ir(CO)(PPh3){N(Ph2PS)(2)}] with MeI afforded [Ir(Me)(I)(CO)(PPh3)(N(Ph2PS)(2)}]. Treatment of [Ir(COE)(2)Cl](2) with K[N(R2PO)(2)] afforded [Ir(COE)(2){N(Ph2PO)(2)}] that reacted with MeOTf (OTf = triffate) to give [Ir{N(Ph2PO)(2)}(COE)(2)(Me)(OTf)]. The crystal structures of [Ir(CO)(PPh3){N(Ph2PS)(2)}], [M(COD){N(Ph2PS)(2)}] (M = Ir, Rh), [Ir(ol)(2){N((Pr2PS)-P-i)(2)}](ol = COE, C2H4), trans-[Ir(H)(Cl)(COD){N(Ph2PS)(2)}], and [Ir(COE)(2){N(Ph2PO)(2)}] have been determined. (c) 2005 Elsevier B.V. All rights reserved.