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Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide
Sindlinger, C.P.; Lawrence, S.R.; Cordes, D.B.; Slawin, A.M.Z.; Stasch, A. Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide. Inorganics2017, 5, 29.
Sindlinger, C.P.; Lawrence, S.R.; Cordes, D.B.; Slawin, A.M.Z.; Stasch, A. Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide. Inorganics 2017, 5, 29.
Sindlinger, C.P.; Lawrence, S.R.; Cordes, D.B.; Slawin, A.M.Z.; Stasch, A. Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide. Inorganics2017, 5, 29.
Sindlinger, C.P.; Lawrence, S.R.; Cordes, D.B.; Slawin, A.M.Z.; Stasch, A. Methanediide Formation via Hydrogen Elimination in Magnesium versus Aluminium Hydride Complexes of a Sterically Demanding Bis(iminophosphoranyl)methanediide. Inorganics 2017, 5, 29.
Abstract
Substituted bis(iminophosphoranyl)methanes are CH acidic compounds that can form complexes with formally dianionic central carbon centres. The reaction of H2C(Ph2P=NDip)2 (≡ H2L), Dip = 2,6-diisopropylphenyl, with one equivalent of di-n-butylmagnesium afforded the methanide complex [HLMgnBu] 1. Treatment of complex 1 with phenylsilane in aromatic solvents at elevated temperatures afforded the methanediide complex [(LMg)2] 2 presumably via the MgH intermediate [(HLMgH)n] (n = 1 or 2). The reaction of 1 with LiAlH4 in diethyl ether yielded the AlH complex [HLAlH2] 3. Alternatively, this complex was also obtained from the reaction of H2L with AlH3∙NMe3. The molecular structures of [HLMgnBu] 1, [(LMg)2] 2, and [HLAlH2] 3 are reported. Complex 3 shows no sign of H2 elimination to a methanediide species at elevated temperatures in contrast to the facile elimination of the putative reaction intermediate [(HLMgH)n] (n = 1 or 2) to form [(LMg)2] 2. The chemical properties of complex 2 were investigated and this complex appears to be stable against coordination with strong donor molecules.
Chemistry and Materials Science, Inorganic and Nuclear Chemistry
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