Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC_6H_3(OMe-o)(C_3H_5-p)) _2}_2: Synthesis and transition metal complexes

摘要

Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC_6H_3(OMe-o)(C_3H_5-p)) _2}_2 (1) was synthesized by reacting PhN(PCl _2)_2 with eugenol in the presence of triethylamine. The ligand 1 acts as a bidentate chelating ligand toward metal complexes [M(CO) _4(C_5H_(10)NH)_2] forming [M(CO) _4{η~2-PhN{P(OC_6H_3(OMe-o)(C _3H_5-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)(OC_6H_3(OMe-o)(C _3H_5-p))_2}{PhN(H)(P(OC_6H _3(OMe-o)(C_3H_5-p))2)}] (4). Treatment of 1 with gold(I) derivative, [AuCl(SMe_2)] resulted in the formation of a dinuclear complex, [(AuCl)_2{PhN{P(OC_6H _3(OMe-o)(C_3H_5-p))_2}_2}] (5) with a Au···Au distance of 3.118(2) indicating the possibility of aurophilic interactions. An equimolar reaction between 1 and [Ru(η~6-p-cymene)Cl_2]_2 afforded a tri-chloro-bridged bimetallic complex [(η~6-p-cymene)Ru(μ-Cl) _3Ru{PhN(P(OC_6H_3(OMe-o)(C_3H _5-p))_2)_2}Cl] (6). The crystal structures of 1-3 and 5 were established by single crystal X-ray diffraction studies.