Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds

B. Conway, E. Hevia, A.R. Kennedy, R.E. Mulvey, S. Weatherstone

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Synthesised either by an unusual tert - butyl metathesis between tert - butyllithium and a n, s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA ( 5) (DBA = dibenzylamide), Bu-t MgDA ( 6) (DA = diisopropylamide), Bu-t MgHMDS ( 7) ( HMDS = 1,1,1,3,3,3-hexamethyldisilazide), (BuMgTMP)-Mg-t ( 8) (TMP = 2,2,6,6-tetramethylpiperidide) and Bu-t MgNCy2 ( 9) (cy = cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)(2) ring and terminal Bu-t ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu-n MgN(H) Dipp](12) ( 10a) and its monomeric solvate Bu-n MgN( H) Dipp center dot TMEDA ( 10b) ( Dipp = 2,6-diisopropylphenyl; TMEDA = N, N, N, N - tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu-t MgOBut center dot THF (11), Bu-t Mg(mu-OBut) (mu-TMP) MgTMP (12) and Mg(OBun) HMDS center dot solv [solv = THF (13a) or Et2O(13b)], made fortuitously during the course of this work, are also presented.
LanguageEnglish
Pages1532-1544
Number of pages12
JournalDalton Transactions
Volume2005
Issue number8
DOIs
Publication statusPublished - 2005

Fingerprint

Amides
Oxygen
Thymidine Monophosphate
X ray crystallography
Molecular structure
Crystal structure
Sodium
Nuclear magnetic resonance
alkoxyl radical
Crystalline materials
Ligands
Atoms
phenyllithium

Keywords

  • ray crystal-structures
  • 1st structural-characterization
  • inverse crown-ether
  • main group elements
  • metal alkyl
  • solid-state
  • magnesium complexes
  • lithium-magnesium
  • aryl compounds
  • organomagnesium reagents

Cite this

@article{f35d5d5d063c45d48e95ca34b6e351e8,
title = "Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds",
abstract = "Synthesised either by an unusual tert - butyl metathesis between tert - butyllithium and a n, s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA ( 5) (DBA = dibenzylamide), Bu-t MgDA ( 6) (DA = diisopropylamide), Bu-t MgHMDS ( 7) ( HMDS = 1,1,1,3,3,3-hexamethyldisilazide), (BuMgTMP)-Mg-t ( 8) (TMP = 2,2,6,6-tetramethylpiperidide) and Bu-t MgNCy2 ( 9) (cy = cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)(2) ring and terminal Bu-t ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu-n MgN(H) Dipp](12) ( 10a) and its monomeric solvate Bu-n MgN( H) Dipp center dot TMEDA ( 10b) ( Dipp = 2,6-diisopropylphenyl; TMEDA = N, N, N, N - tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu-t MgOBut center dot THF (11), Bu-t Mg(mu-OBut) (mu-TMP) MgTMP (12) and Mg(OBun) HMDS center dot solv [solv = THF (13a) or Et2O(13b)], made fortuitously during the course of this work, are also presented.",
keywords = "ray crystal-structures, 1st structural-characterization, inverse crown-ether, main group elements, metal alkyl, solid-state, magnesium complexes, lithium-magnesium, aryl compounds, organomagnesium reagents",
author = "B. Conway and E. Hevia and A.R. Kennedy and R.E. Mulvey and S. Weatherstone",
year = "2005",
doi = "10.1039/b501502b",
language = "English",
volume = "2005",
pages = "1532--1544",
journal = "Dalton Transactions",
issn = "1477-9226",
number = "8",

}

Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds. / Conway, B.; Hevia, E.; Kennedy, A.R.; Mulvey, R.E.; Weatherstone, S.

In: Dalton Transactions, Vol. 2005, No. 8, 2005, p. 1532-1544.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds

AU - Conway, B.

AU - Hevia, E.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - Weatherstone, S.

PY - 2005

Y1 - 2005

N2 - Synthesised either by an unusual tert - butyl metathesis between tert - butyllithium and a n, s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA ( 5) (DBA = dibenzylamide), Bu-t MgDA ( 6) (DA = diisopropylamide), Bu-t MgHMDS ( 7) ( HMDS = 1,1,1,3,3,3-hexamethyldisilazide), (BuMgTMP)-Mg-t ( 8) (TMP = 2,2,6,6-tetramethylpiperidide) and Bu-t MgNCy2 ( 9) (cy = cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)(2) ring and terminal Bu-t ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu-n MgN(H) Dipp](12) ( 10a) and its monomeric solvate Bu-n MgN( H) Dipp center dot TMEDA ( 10b) ( Dipp = 2,6-diisopropylphenyl; TMEDA = N, N, N, N - tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu-t MgOBut center dot THF (11), Bu-t Mg(mu-OBut) (mu-TMP) MgTMP (12) and Mg(OBun) HMDS center dot solv [solv = THF (13a) or Et2O(13b)], made fortuitously during the course of this work, are also presented.

AB - Synthesised either by an unusual tert - butyl metathesis between tert - butyllithium and a n, s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA ( 5) (DBA = dibenzylamide), Bu-t MgDA ( 6) (DA = diisopropylamide), Bu-t MgHMDS ( 7) ( HMDS = 1,1,1,3,3,3-hexamethyldisilazide), (BuMgTMP)-Mg-t ( 8) (TMP = 2,2,6,6-tetramethylpiperidide) and Bu-t MgNCy2 ( 9) (cy = cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)(2) ring and terminal Bu-t ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu-n MgN(H) Dipp](12) ( 10a) and its monomeric solvate Bu-n MgN( H) Dipp center dot TMEDA ( 10b) ( Dipp = 2,6-diisopropylphenyl; TMEDA = N, N, N, N - tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu-t MgOBut center dot THF (11), Bu-t Mg(mu-OBut) (mu-TMP) MgTMP (12) and Mg(OBun) HMDS center dot solv [solv = THF (13a) or Et2O(13b)], made fortuitously during the course of this work, are also presented.

KW - ray crystal-structures

KW - 1st structural-characterization

KW - inverse crown-ether

KW - main group elements

KW - metal alkyl

KW - solid-state

KW - magnesium complexes

KW - lithium-magnesium

KW - aryl compounds

KW - organomagnesium reagents

UR - http://www.rsc.org/ej/DT/2005/b501502b.pdf

UR - http://dx.doi.org/10.1039/b501502b

U2 - 10.1039/b501502b

DO - 10.1039/b501502b

M3 - Article

VL - 2005

SP - 1532

EP - 1544

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 8

ER -