Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide

Christian P. Sindlinger; Samuel R. Lawrence; David B. Cordes; Alexandra M. Z. Slawin; Andreas Stasch

doi:10.3390/inorganics5020029

Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide

Christian P. Sindlinger, Samuel R. Lawrence, David B. Cordes, Alexandra M. Z. Slawin, Andreas Stasch

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Journal	Inorganics
Volume	5
Issue number	2
Early online date	22 Apr 2017
DOIs	https://doi.org/10.3390/inorganics5020029
Publication status	Published - Jun 2017

Keywords

Alane
Aluminium
Hydrogen formation
Magnesium
Magnesium hydride
Metal hydrides
Methanediides
N,N′-chelation

Access to Document

10.3390/inorganics5020029Licence: CC BY

Stasch_2017_Inorganics_Methanediide_CCBY-VoR
© 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/).
Final published version, 2.2 MBLicence: CC BY

Cite this

@article{4cebcc9130d24f7b890a0199d459fb2d,

title = "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.",

keywords = "Alane, Aluminium, Hydrogen formation, Magnesium, Magnesium hydride, Metal hydrides, Methanediides, N,N′-chelation",

author = "Sindlinger, {Christian P.} and Lawrence, {Samuel R.} and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Andreas Stasch",

year = "2017",

month = jun,

doi = "10.3390/inorganics5020029",

language = "English",

volume = "5",

journal = "Inorganics",

issn = "2304-6740",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

number = "2",

}

TY - JOUR

T1 - Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide

AU - Sindlinger, Christian P.

AU - Lawrence, Samuel R.

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Stasch, Andreas

PY - 2017/6

Y1 - 2017/6

N2 - 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.

AB - 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.

KW - Alane

KW - Aluminium

KW - Hydrogen formation

KW - Magnesium

KW - Magnesium hydride

KW - Metal hydrides

KW - Methanediides

KW - N,N′-chelation

UR - http://www.mdpi.com/2304-6740/5/2/29/s1

U2 - 10.3390/inorganics5020029

DO - 10.3390/inorganics5020029

M3 - Article

SN - 2304-6740

VL - 5

JO - Inorganics

JF - Inorganics

IS - 2

ER -

Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide

Abstract

Keywords

Access to Document

Other files and links

Fingerprint