Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide
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.
Citation
Sindlinger , C P , Lawrence , S R , Cordes , D B , Slawin , A M Z & Stasch , A 2017 , ' Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide ' , Inorganics , vol. 5 , no. 2 . https://doi.org/10.3390/inorganics5020029
Publication
Inorganics
Status
Peer reviewed
ISSN
2304-6740Type
Journal article
Rights
© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
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