Iridium and rhodium complexes containing dichalcogenoimidodiphosphinato ligands

Treatment of [MCl(CO)(PPh3)2] with K[N(R2PQ)2] afforded [M{N(Ph2PQ)2}(CO)(PPh3)] (M = Ir, Rh; Q = S, Se). The IR C=O stretching frequencies for [M(CO)(PPh3){N(Ph2PQ)2}] were found to decrease in the order S > Se. Treatment of [M(COD)Cl]2 with K[N(Ph2PQ)2] afforded [M(COD){N(Ph2PQ)2}] (COD = 1,5-cyclooctadiene; M = Ir, Rh; Q = S, Se). Treatment of [Ir(ol)2Cl] with K[N(Pr2iPQ)2] afforded [Ir(ol)2{N(Pr2iPQ)2}]2 (ol = cyclooctene COE, C2H4; Q = S, Se). Oxidative addition of [Ir(CO)(PPh3){N(Ph2PS)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)2Cl]2 with K[N(R2PO)2] afforded [Ir(COE)2{N(Ph2PO)2}] that reacted with MeOTf (OTf = triflate) 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(Pr2iPS)2}](ol = COE, C2H4), trans-[Ir(H)(Cl)(COD){N(Ph2PS)2}], and [Ir(COE)2{N(Ph2PO)2}] have been determined.

Graphical abstractIr(I) and Rh(I) dichalcogenoimidodiphosphinato complexes of the types [M(CO)(PPh3){N(Ph2PQ)2}], [M(COD){N(Ph2PQ)2}], and [Ir(ol)2{N(Pr2iPQ)2}](M=Ir,Rh;Q=O,S,Se;ol=cyclooctene,C2H4) have been synthesized. Oxidative addition of the Ir(I) dichalcogenoimidodiphosphinato complexes with MeI and HCl has been studied.Figure optionsDownload full-size imageDownload as PowerPoint slide