A molybdenum complex bearing a tetraphosphine ligand as a precursor for heterobimetallic complexes

作者：Yasuda Ryoga; Iwasa Kentaro; Niikura Fumiya; Seino Hidetake^*; Mizobe Yasushi

来源：Dalton Transactions, 2014, 43(24): 9344-9355.

DOI：10.1039/c4dt00581c

The reactions of [CpMoH(kappa(3)-P4)] (2; P4 = meso-o-C6H4(PPhCH2CH2PPh2)(2)) with protic acids gave [CpMo(kappa(4)-P4)](+) (4(+)) via the intermediary formation of [CpMoH2(kappa(3)-P4)](+). Treatment of 2 with iodine provided the cationic complex [CpMoHI(kappa(3)-P4)][I] (5[I]). Early-late heterobimetallic complexes of the type [CpMoH(mu-P4-1 kappa(3):2 kappa)MLnCl] (MLn = Ru(Hmb)Cl (6), Ir(eta(5)-C5Me5)Cl (7), Rh(cod), Ir(cod), Pd(eta(3)-C3H5) (10); Hmb = eta(6)-C6Me6, cod = eta(4)-1,5-cyclooctadiene) were synthesised by reacting 2 with [MLn(mu-Cl)](2), and their structures were characterised by NMR spectroscopy. The hydride ligand in 6 was replaced by chloride in chlorinated organic solvents to give [CpMoCl(mu-P4-1 kappa(3):2)Ru(Hmb)Cl-2] (11). Self-reaction of 10 produced allylbenzene and [CpMo(mu-H){mu-PhP(CH2)(2)P(Ph)-o-C6H4-P(Ph)(CH2)(2)PPh2-1 kappa(3):2 kappa(2)}PdCl] (12), in which the Mo-Pd edge was bridged by a hydride ligand and the phosphide moiety emerged from the loss of one phenyl group. The molecular structures of 4[Cl], 4[OTf], 5[I], 6, 7, 11, and 12 were established by single-crystal X-ray analysis.

• 出版日期2014