Synthesis and crystal structure of the new heteroleptic magnesium bis(amide) [{Mg[mu-N(H)Ph][N(SiMe3)(2)]center dot THF}(2)], and density functional MO calculations on model systems

D.R. Armstrong, W. Clegg, R.E. Mulvey, R.B. Rowlings

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Abstract

Reaction of Mg[N(SiMe3)(2)](2) with one molar equivalent of the primary amine PhNH2 in THF solution gave the transaminated THF-solvated heteroleptic bis(amide) [{Mg[mu -N(H)Ph][N(SiMe3)(2)]. THF}(2)]. In the crystalline state the new amide is dimeric with a central, planar azamagnesacyclic (NMg)(2) ring. The resonance stabilised anilido units prefer to bridge to the magnesium centres whereas the bulkier secondary hexamethyldisilazanzide groups occupy terminal sites. Terminal solvation by THF completes the distorted tetrahedral environment about magnesium. Comparisons of this structure with other crystallographically characterised heteroleptic magnesium bis(amides) are made. The interesting, almost square geometry of this (NMg)(2) ring has also prompted a density functional MO study on magnesium systems and related molecules of Groups 1, 2 and 13, the results of which are also reported.
LanguageEnglish
Pages409-413
Number of pages4
JournalJournal of the Chemical Society, Dalton Transactions
Volume2001
Issue number4
DOIs
Publication statusPublished - 2001

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Amides
Magnesium
Density functional theory
Crystal structure
Solvation
Amines
Crystalline materials
Molecules
Geometry

Keywords

  • molecular orbital methods
  • basis sets
  • lithium anilide
  • complexes
  • intermediate
  • benzonitrile
  • chemistry
  • compound

Cite this

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title = "Synthesis and crystal structure of the new heteroleptic magnesium bis(amide) [{Mg[mu-N(H)Ph][N(SiMe3)(2)]center dot THF}(2)], and density functional MO calculations on model systems",
abstract = "Reaction of Mg[N(SiMe3)(2)](2) with one molar equivalent of the primary amine PhNH2 in THF solution gave the transaminated THF-solvated heteroleptic bis(amide) [{Mg[mu -N(H)Ph][N(SiMe3)(2)]. THF}(2)]. In the crystalline state the new amide is dimeric with a central, planar azamagnesacyclic (NMg)(2) ring. The resonance stabilised anilido units prefer to bridge to the magnesium centres whereas the bulkier secondary hexamethyldisilazanzide groups occupy terminal sites. Terminal solvation by THF completes the distorted tetrahedral environment about magnesium. Comparisons of this structure with other crystallographically characterised heteroleptic magnesium bis(amides) are made. The interesting, almost square geometry of this (NMg)(2) ring has also prompted a density functional MO study on magnesium systems and related molecules of Groups 1, 2 and 13, the results of which are also reported.",
keywords = "molecular orbital methods, basis sets, lithium anilide, complexes, intermediate, benzonitrile, chemistry, compound",
author = "D.R. Armstrong and W. Clegg and R.E. Mulvey and R.B. Rowlings",
year = "2001",
doi = "10.1039/b008756o",
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journal = "Journal of the Chemical Society, Dalton Transactions",
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TY - JOUR

T1 - Synthesis and crystal structure of the new heteroleptic magnesium bis(amide) [{Mg[mu-N(H)Ph][N(SiMe3)(2)]center dot THF}(2)], and density functional MO calculations on model systems

AU - Armstrong, D.R.

AU - Clegg, W.

AU - Mulvey, R.E.

AU - Rowlings, R.B.

PY - 2001

Y1 - 2001

N2 - Reaction of Mg[N(SiMe3)(2)](2) with one molar equivalent of the primary amine PhNH2 in THF solution gave the transaminated THF-solvated heteroleptic bis(amide) [{Mg[mu -N(H)Ph][N(SiMe3)(2)]. THF}(2)]. In the crystalline state the new amide is dimeric with a central, planar azamagnesacyclic (NMg)(2) ring. The resonance stabilised anilido units prefer to bridge to the magnesium centres whereas the bulkier secondary hexamethyldisilazanzide groups occupy terminal sites. Terminal solvation by THF completes the distorted tetrahedral environment about magnesium. Comparisons of this structure with other crystallographically characterised heteroleptic magnesium bis(amides) are made. The interesting, almost square geometry of this (NMg)(2) ring has also prompted a density functional MO study on magnesium systems and related molecules of Groups 1, 2 and 13, the results of which are also reported.

AB - Reaction of Mg[N(SiMe3)(2)](2) with one molar equivalent of the primary amine PhNH2 in THF solution gave the transaminated THF-solvated heteroleptic bis(amide) [{Mg[mu -N(H)Ph][N(SiMe3)(2)]. THF}(2)]. In the crystalline state the new amide is dimeric with a central, planar azamagnesacyclic (NMg)(2) ring. The resonance stabilised anilido units prefer to bridge to the magnesium centres whereas the bulkier secondary hexamethyldisilazanzide groups occupy terminal sites. Terminal solvation by THF completes the distorted tetrahedral environment about magnesium. Comparisons of this structure with other crystallographically characterised heteroleptic magnesium bis(amides) are made. The interesting, almost square geometry of this (NMg)(2) ring has also prompted a density functional MO study on magnesium systems and related molecules of Groups 1, 2 and 13, the results of which are also reported.

KW - molecular orbital methods

KW - basis sets

KW - lithium anilide

KW - complexes

KW - intermediate

KW - benzonitrile

KW - chemistry

KW - compound

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DO - 10.1039/b008756o

M3 - Article

VL - 2001

SP - 409

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JO - Journal of the Chemical Society, Dalton Transactions

T2 - Journal of the Chemical Society, Dalton Transactions

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