The compound [Mo(CO)3(η-C5Me5)]BF4 reacts with π acids, L [L = PPh3, P(OMe)3, CO, or p-MeC6H4NC], giving the 18 electron cations [Mo(CO)3(η-C5Me5)L]+. The complex [Mo(CO)3(η-C5Me5)(PPh3)]BF4 (1) has been characterized by a single-crystal X-ray diffraction study. The reaction of (1) with one equivalent of Na[BH4] gives the neutral metal formyl complex [Mo(CO)2(η-C5Me5)(PPh3)(CHO)], (2), which, in solution, converts to [MoH(CO)3(η-C5Me5)] above –40 °C. If [Mo(CO)3(η-C5Me5){P(OMe)3}]BF4, (3), is used instead of (1), the reduction in methanol solution with Na[BH4] allows isolation of the thermally stable cis-[Mo(CO)2(η-C5Me5){P(OMe)3}(CHO)], (4). Thermal decomposition of (4) in methanol solution at room temperature is slow and gives cis-[MoH(CO)2(η-C5Me5){P(OMe)3}]. This result emphasizes that the great difference observed in the thermal stability of complexes (2) and (4) is attributable to different decomposition pathways.

Reactivity of Cationic Molybdenum(II) Complexes. Part 1. Hydride Reduction of the 18 Electron Complexes [Mo(CO)3(eta-C5Me5)] + [L=PPh3 or P(OMe)3] and Isolation of the Thermally Stable Formil Complex cis-[Mo(CO)2(eta-C5Me5){P(OMe)3}(CHO)] Crystal Structure of [Mo(CO)(eta-C5Me5)(PPh3)]BF4.0.5MeOH

LEONI, PIERO;PASQUALI, MARCO;MARCHETTI, FABIO;
1988

Abstract

The compound [Mo(CO)3(η-C5Me5)]BF4 reacts with π acids, L [L = PPh3, P(OMe)3, CO, or p-MeC6H4NC], giving the 18 electron cations [Mo(CO)3(η-C5Me5)L]+. The complex [Mo(CO)3(η-C5Me5)(PPh3)]BF4 (1) has been characterized by a single-crystal X-ray diffraction study. The reaction of (1) with one equivalent of Na[BH4] gives the neutral metal formyl complex [Mo(CO)2(η-C5Me5)(PPh3)(CHO)], (2), which, in solution, converts to [MoH(CO)3(η-C5Me5)] above –40 °C. If [Mo(CO)3(η-C5Me5){P(OMe)3}]BF4, (3), is used instead of (1), the reduction in methanol solution with Na[BH4] allows isolation of the thermally stable cis-[Mo(CO)2(η-C5Me5){P(OMe)3}(CHO)], (4). Thermal decomposition of (4) in methanol solution at room temperature is slow and gives cis-[MoH(CO)2(η-C5Me5){P(OMe)3}]. This result emphasizes that the great difference observed in the thermal stability of complexes (2) and (4) is attributable to different decomposition pathways.
Leoni, Piero; Aquilini, E; Pasquali, Marco; Marchetti, Fabio; Sabat, M.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/206425
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