1266740-33-3Relevant academic research and scientific papers
Preparation and reactions of molybdenum and tungsten hydride complexes containing the tetraphosphane ligand meso-o-C6H 4(PPhCH2CH2PPh2)2
Dai, Qi Xiu,Seino, Hidetake,Mizobe, Yasushi
, p. 141 - 149 (2011)
The reaction of [Mo(κ2-dppe)(κ4-P4)] (1a) {dppe = PPh2CH2CH2PPh2, P4 = meso-o-C6H4(PPhCH2CH2PPh 2)2} with 1 atm of H2 at room temperature selectively gave [MoH2(κ2-dppe)(κ3- P4)] (3a). The W analogue of 1a reacted with 1 atm of H2 at 80 °C to form a mixture of [WH2(κ2-dppe) (κ3-P4)] and [WH4(κ4-P4)] (5b), the latter of which could be cleanly prepared by the reduction of [WBr 2(κ4-P4)] with NaBH4 in ethanol at 50 °C. The molecular structure of complex 5b differed from that of the related complex [WH4(dppe)2] and showed much higher reactivity. Insertion into the W-H bonds took place in the reaction of 5b with CS 2 at 50 °C to give the methylenedithiolate complex [W(κ2-S2CH2)(κ4-P4)] (6) as the sole product, and the hydride ligands in 5b were replaced by isocyanides at 80 °C to form [W(CNR)2(κ4-P4)] {R = tBu (7), 2,6-Me2C6H3 (8)} in moderate yields. The detailed structures were determined by X-ray crystallography for 3a, 5b, 6, and 7, while the fluxional behavior of 3a in solution was clarified by variable-temperature NMR (VT NMR) spectroscopic studies. Reaction of [WBr 2(κ4-P4)] {P4 = meso-o-C6H 4(PPhCH2CH2PPh2)2} with NaBH4 in ethanol at 50 °C forms [WH4(κ 4-P4)], which is one of the rare examples of a polyhydride complex containing a tetraphosphane co-ligand. Structure determination by single-crystal X-ray analysis and the reactivity of the complex towards CS2 and RNC are reported. Copyright
