Bisamino(diphosphonite) with dangling olefin functionalities: synthesis, metal chemistry and catalytic utility of Rh~I and Pd~(II) complexes in hydroformylation and Suzuki-Miyaura reactions

摘要

Bisamino(diphosphonite), p-C_6H_4{N{P(OC_6H_4C_3H_5-o)_2}_2}_2 (1), was prepared by reacting p-C_6H_4- {N(PCl_2)_2}_2 with four equivalents of o-allylphenol in 85% yield. Compound 1 on treatment with [M(CO)_4(HNC_5H_(10))_2] (M = Mo or W) gave cis-[{M(CO)_4}_2{p-C_6H_4{N(P(OC_6H_4C_3H_5-o)_2)_2}_2}] (2, M = Mo; 3, M = W). The reaction of 1 with [Fe(η~5-C_5H_5)(CO)_2]_2 yielded the complex [{Fe(η~5-C_5H_5)(μ-CO)}_2{p-C_6H_4{N(P- (OC_6H_4C_3H_5-o)_2)_2}_2}] (4). Treatment of 1 with Fe(CO)_5 furnished a mononuclear complex, [{Fe(CO)_3}_2- {p-C_6H_4{N{P(OC_6H_4C_3H_5-o)_2}_2}_2}] (5). The ruthenium(II) complex, [{(η~6-p-cymene)Ru(μ-Cl)_3RuCl}_2{p-C_6H_4- {N(P(OC_6H_4C_3H_5-o)_2)_2}_2}] (6), was obtained on treatment of ligand 1 with [(η~6-p-cymene)Ru(Cl)_2]_2. The reaction between 1 and [Rh(COD)Cl]_2 (COD = 1,5-cyclooctadiene) in dichloromethane resulted in the formation of a dinuclear complex [{RhCl}_2{p-C_6H_4{N(P(OC_6H_4C_3H_5-o)_2)_2}_2}] (7), in which the allyl double bond of one of the phenoxy groups coordinates to the metal center. When ligand 1 was reacted with two equivalents of [Pd(COD)Cl_2], a dinuclear complex [{PdCl_2}_2{p-C_6H_4{N(P(OC_6H_4C_3H_5-o)_2)_2}_2}] (8) was obtained. With copper(I) halides, ligand 1 afforded tetranuclear complexes, [{(Cu(μ-X)(NCCH_3))_2}_2- {p-C_6H_4{N(P(OC_6H_4C_3H_5-o)_2)_2}_2}] (9, X = Cl; 10, X = Br; 11, X = I). Reaction of 1 with four equivalents of [AuCl(SMe_2)] produced a tetranuclear complex, [(AuCl)_4{p-C_6H_4{N{P(OC_6H_4C_3H_5-o)_2}_2}_2}] (12). Complex 8 shows excellent catalytic activity in the Suzuki-Miyaura cross-coupling reaction under microwave conditions and complex 7 catalyzes hydroformylation of styrenes with good TONs.