Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC6H3(OMe-o)(C3H5-p))2}2: Synthesis and transition metal complexes

Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC6H3(OMe-o)(C3H5-p))2}2 (1) was synthesized by reacting PhN(PCl2)2 with eugenol in the presence of triethylamine. The ligand 1 acts as a bidentate chelating ligand toward metal complexes [M(CO)4(C5H10NH)2] forming [M(CO)4{η2-PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (M = Mo, 2; W, 3). The reaction between 1 and [CpFe(CO)2]2 leads to the cleavage of one of the P–N bonds due to the metal assisted hydrolysis to give a mononuclear complex [CpFe(CO){P(O)(OC6H3(OMe-o)(C3H5-p))2}{PhN(H)(P(OC6H3(OMe-o)(C3H5-p))2)}] (4). Treatment of 1 with gold(I) derivative, [AuCl(SMe2)] resulted in the formation of a dinuclear complex, [(AuCl)2{PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (5) with a Au···Au distance of 3.118(2) Å indicating the possibility of aurophilic interactions. An equimolar reaction between 1 and [Ru(η6-p-cymene)Cl2]2 afforded a tri-chloro-bridged bimetallic complex [(η6-p-cymene)Ru(μ-Cl)3Ru{PhN(P(OC6H3(OMe-o)(C3H5-p))2)2}Cl] (6). The crystal structures of 1–3 and 5 were established by single crystal X-ray diffraction studies.