The Iminophosphorane‐Phosphane Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

Abstract

AbstractThe iminophosphorane‐phosphane ligand Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2 (1) has been synthesized by partial imination of bis[2‐(diphenylphosphanyl)phenyl] ether (DPEphos) with phosphoryl azide (PhO)2P(O)N3. A similar reaction in a 1:2 stoichiometry affords the bis(iminophosphorane) O{C6H4PPh2=NP(O)(OPh)2}2 (2). The chalcogen derivatives O{C6H4P(E)Ph2}2 [E = S (3) and Se (4)] and Ph2P(E)C6H4OC6H4PPh2=NP(O)(OPh)2 [E = S (5) and Se (6)] are also synthesized by treating DPEphos and 1 with elemental sulfur and selenium, respectively. The mononuclear complexestrans‐[MCl2{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2][M = Pt (7) Pd (8)] and trans‐[Rh(CO)Cl{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2] (12) are prepared by the reaction of 1 with [Pt(COD)Cl2], [Pd(COD)Cl2], and [{Rh(CO)2Cl}2], respectively. Treatment of 1 with [Pd2(dba3)] (dba = dibenzylideneacetone) affords the mononuclear complex [Pd0{κ2‐P,O‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2] (9) in which ligand 1 coordinates through its P and O centers in a κ2‐P,O chelating fashion. The monocoordinated AuI complex [AuCl{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}] (10) has been prepared by the reaction of 1 and [AuCl(SMe2)] and its structure has been confirmed by X‐ray crystallography. The reaction of 1 with [{Rh(COD)Cl}2] in the presence of AgOTf affords the cationic RhI complex cis‐[Rh(COD){κ2‐P,O‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}][OTf] (11). The catalytic activity of the Pd0 complex 9 has been investigated in Suzuki cross‐coupling reactions. Homogeneous catalytic hydrogenation of olefins has also been studied using the cationic RhI complex 11.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)