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Reaction of BH4- with Mo2Cp 2(μ-SMe)n species to give tetrahydroborato, hydrido or dimetallaborane compounds: Control of product by ancillary ligands

Abstract : The reaction of mono- or dichloro-dimolybdenum(m) complexes [Mo 2Cp2(μ-SMe)2(μ-Cl)(μ-Y)] (Cp=η5-C5H5; 1, Y = SMe; 2, Y = PPh 2; 3, Y = Cl) with NaBH4, at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives 8 and 12 has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the μ-azavinylidene derivative [Mo 2Cp2(μ-SMe)2(μ-PPh2)(μ-N= CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4, with nitrile derivatives, [Mo2Cp 2(μ-SMe)4-n(CH3CN)2n] n+ (5, n= 1; 6 =2), afforded the tetrahydroborato compound 8, together with a μ-azavinylidene species [Mo2Cp2(μ- SMe)3(μ-N=CHMe)] (14), when n= 1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo 2Cp2(μ-SMe)2(μ-BH4)(μ-N= CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(μ-SMe)2(μ-X)-(μ-Y)] (1, X/Y = Cl/SMe; 2, X/Y = Cl/PPh2; 4, X/Y = SMe/PPh2).
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https://hal.univ-brest.fr/hal-01763874
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Submitted on : Wednesday, April 11, 2018 - 2:58:27 PM
Last modification on : Thursday, October 3, 2019 - 8:50:02 AM

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Nolwenn Cabon, François Pétillon, Philippe Schollhammer, Jean Talarmin, K.W. Muir. Reaction of BH4- with Mo2Cp 2(μ-SMe)n species to give tetrahydroborato, hydrido or dimetallaborane compounds: Control of product by ancillary ligands. Dalton Transactions, Royal Society of Chemistry, 2004, pp.2708-2719. ⟨10.1039/b407564a⟩. ⟨hal-01763874⟩

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