Synthesis and structural studies of RhI, PdI, NiII complexes and one-pot synthesis of binuclear RuII complex [(η6-p-cymene)Ru(μ2-Cl)3Ru{PhN(P(OC6H4OMe-o)2)2}Cl]

The RhI, RuII, PdI and NiII complexes of the aminobis(phosphonite), PhN(P(OC6H4OMe-o)2)2 (1) are reported. The reactions of 1 with [Rh(COD)Cl]2 in 1:1 and 2:1 molar ratio afford the mono- and diolefin substituted chloro bridged chelate complexes, [(COD)Rh2(μ2-Cl)2{PhN(P(OC6H4OMe-o)2)2}] (2) and [Rh(μ2-Cl){PhN(P(OC6H4OMe-o)2)2}]2 (3), respectively. Similarly, the cationic mono- and bis-chelate complexes, [Rh(COD){PhN(P(OC6H4OMe-o)2)2}]OTf (4) and [Rh{PhN(P(OC6H4OMe-o)2)2}2]OTf (5) are obtained by treating 1 with [Rh(COD)Cl]2 in the presence of AgOTf in appropriate ratios. The dinuclear RhI carbonyl complex, [RhCl(CO){μ-PhN(P(OC6H4OMe-o)2)2}]2 (6) is prepared by treating 1 with 0.5 equiv. of [Rh(CO)2Cl]2. Reaction of 1 with cis-[NiBr2(DME)] (DME = 1,2-dimethoxyethane) affords [{PhN(P(OC6H4OMe-o)2)2}NiBr2] (7) whereas with [Ru-(η6-p-cymene)Cl2]2 in refluxing THF medium produces an interesting and rare bimetallic RuII complex, [(η6-p-cymene)Ru(μ2-Cl)3Ru{PhN(P(OC6H4OMe-o)2)2}Cl] (8). Redox condensation of the Pd0 and PdII derivatives with 1 affords the dinuclear PdI complex, [PdBr{μ-PhN(P(OC6H4OMe-o)2)2}]2 (9). The formation and structure of complexes 2–9 are assigned through various spectroscopic and micro analysis data. The molecular structures of 5 and 7–9 are confirmed by single crystal X-ray diffraction studies.