Preparation and Reactions of Molybdenum and Tungsten Hydride Complexes Containing the Tetraphosphane Ligand meso ‐ o ‐C 6 H 4 (PPhCH 2 CH 2 PPh 2 ) 2

Autor: Qi Xiu Dai, Yasushi Mizobe, Hidetake Seino
Rok vydání: 2010
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2011:141-149
ISSN: 1099-0682
1434-1948
Popis: The reaction of [Mo(κ 2 -dppe)(κ 4 -P4)] (1a) {dppe = PPh 2C H 2 CH 2 PPh 2 , P4 = meso-o-C 6 H 4 (PPhCH 2 CH 2 PPh 2 ) 2 } with 1 atm of H 2 at room temperature selectively gave [MoH 2 (κ 2 -dppe)(κ 3 -P4)] (3a). The W analogue of 1a reacted with 1 atm of H 2 at 80 °C to form a mixture of [WH 2 (κ 2 -dppe)-(κ 3 -P4)] and [WH 4 (κ 4 -P4)] (5b), the latter of which could be cleanly prepared by the reduction of [WBr 2 (κ 4 -P4)] with NaBH 4 in ethanol at 50 °C. The molecular structure of complex 5b differed from that of the related complex [WH 4 -(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(κ 2 -S 2 CH 2 )(κ 4 -P4)] (6) as the sole product, and the hydride ligands in 5b were replaced by isocyanides at 80 °C to form [W(CNR) 2 (κ 4 -P4)] {R = tBu (7), 2,6-Me 2 C 6 H 3 (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.
Databáze: OpenAIRE
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