Molybdenum and Tungsten Nitrosyl Complexes in Hydrogen Activation

• Published in: European Journal of Inorganic Chemistry 2010-07, Vol.2010 (21), p.3328-3337
• Main Authors: Dybov, Alexander, Blacque, Olivier, Berke, Heinz
• Format: Article
• Language: English
• Subjects: Homogeneous catalysis; Hydrides; Hydrogen activation; Hydrogenation; Molybdenum; Tungsten
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201000301

Two transition‐metal hydride complexes of the type [M(dippe)2(NO)(H)] [M = W (2a), Mo (2b); dippe = 1,2‐bis(diisopropylphosphanyl)ethane] have been prepared by the reaction of [M(dippe)2(NO)(Cl)] [M = W (1a), Mo (1b)] with LiBH4. The nitrosyl groups of the tungsten complexes 1a and 2a are capable to coordinate a LiBH4 molecule to form the stable adducts W(dippe)2(Cl)(NO···LiBH4) (1c) and W(dippe)2(H)(NO···LiBH4) (2c). Addition of ethylenediamine to a toluene solution of 2c led to rupture of the 2c adduct and afforded 2a in good yield. After the interaction of 2a with [H(Et2O)][BF4], the stable seven‐coordinated cationic dihydride [W(dippe)(H)2(dippe)(NO)][BF4] (6a) was isolated. The reaction between 2b and [H(Et2O)][BF4] led to the formation of [Mo(dippe)2(NO)(FBF3)] (6b) in which BF4– was found to be coordinated to the metal centre. The [H(Et2O)2][BArF4] [ArF = 3,5‐(CF3)2C6H3] acid interacted with 2a to yield the seven‐coordinated complex [W(dippe)(H)2(dippe)(NO)][BArF4] (5a) similar to 6a. In the reaction between 2b and [H(Et2O)2][BArF4], the 16e– five‐coordinated complex [Mo(dippe)2(NO)][BArF4] (4b) was formed. X‐ray diffraction revealed that 4a has a weak agostic interaction trans to the NO ligand. Complex 4b was found to react rapidly with hydrogen gas under ambient conditions to form the dihydride complex [Mo(dippe)(H)2(dippe)(NO)][BArF4] (5b), which is unstable in the absence of a hydrogen atmosphere. The equilibrium constant for the reversible reaction of 4b with hydrogen was found to be K = 2.6 bar–1 at 25 °C. Complex 4b was tested as a catalyst for acetone hydrogenation; a maximum TON of 7 was found. [H(Et2O)2][BArF4] interacts with tungsten hydride to form stable dihydride species. The [Mo(dippe)2NO][BArF4] complex was isolated after reaction with the molybdenum hydride. [Mo(dippe)2NO][BArF4] reacts with hydrogen gas to form a dihydride complex, which is unstable in the absence of H2 needed for equilibration. The dihydride is structurally similar to the tungsten complex.