The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine

W Clegg, L Horsburgh, S T Liddle, F M Mackenzie, Robert Mulvey, A Robertson

Research output: Contribution to journalArticle

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Abstract

A family of crystalline lithium anilide solvates, [{PhN(H)Li .(pyr)(2)}(2)] 1, [{PhN(H)Li .(4-Me-pyr)(2)}(2)] 2 and [{PhN(H)Li}(4).(4-Bu-t-pyr)(6)] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane-toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N-Li](2) ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N-Li](2) transoid ring, separating two mixed ligand [(anilido)N-Li-(pyr)N-Li] rings, made possible by the unusual mu-bonding of a 4-tert-butylpyridine ligand. A combination of H-1, Li-7 and C-13 NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [H-2(8)]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300-193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.

LanguageEnglish
Pages1225-1231
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Volume7
DOIs
Publication statusPublished - 2000

Fingerprint

Anilides
Solvation
Lithium
Toluene
Ligands
Conformations
Crystalline materials
Hexanes
Amides
Molecular structure
Nuclear magnetic resonance
X rays
Atoms
4-tert-butylpyridine
4-methylpyridine
pyridine
Temperature

Keywords

  • amide ladder structures
  • crystal structures
  • adducts
  • dimers

Cite this

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title = "The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine",
abstract = "A family of crystalline lithium anilide solvates, [{PhN(H)Li .(pyr)(2)}(2)] 1, [{PhN(H)Li .(4-Me-pyr)(2)}(2)] 2 and [{PhN(H)Li}(4).(4-Bu-t-pyr)(6)] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane-toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N-Li](2) ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N-Li](2) transoid ring, separating two mixed ligand [(anilido)N-Li-(pyr)N-Li] rings, made possible by the unusual mu-bonding of a 4-tert-butylpyridine ligand. A combination of H-1, Li-7 and C-13 NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [H-2(8)]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300-193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.",
keywords = "amide ladder structures, crystal structures, adducts, dimers",
author = "W Clegg and L Horsburgh and Liddle, {S T} and Mackenzie, {F M} and Robert Mulvey and A Robertson",
year = "2000",
doi = "10.1039/B000576M",
language = "English",
volume = "7",
pages = "1225--1231",
journal = "Journal of the Chemical Society, Dalton Transactions",
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The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine. / Clegg, W ; Horsburgh, L ; Liddle, S T ; Mackenzie, F M ; Mulvey, Robert; Robertson, A .

In: Journal of the Chemical Society, Dalton Transactions, Vol. 7, 2000, p. 1225-1231.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The changing structural chemistry of lithium anilide on solvation by pyridine, 4-methylpyridine or 4-tert-butylpyridine

AU - Clegg, W

AU - Horsburgh, L

AU - Liddle, S T

AU - Mackenzie, F M

AU - Mulvey, Robert

AU - Robertson, A

PY - 2000

Y1 - 2000

N2 - A family of crystalline lithium anilide solvates, [{PhN(H)Li .(pyr)(2)}(2)] 1, [{PhN(H)Li .(4-Me-pyr)(2)}(2)] 2 and [{PhN(H)Li}(4).(4-Bu-t-pyr)(6)] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane-toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N-Li](2) ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N-Li](2) transoid ring, separating two mixed ligand [(anilido)N-Li-(pyr)N-Li] rings, made possible by the unusual mu-bonding of a 4-tert-butylpyridine ligand. A combination of H-1, Li-7 and C-13 NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [H-2(8)]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300-193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.

AB - A family of crystalline lithium anilide solvates, [{PhN(H)Li .(pyr)(2)}(2)] 1, [{PhN(H)Li .(4-Me-pyr)(2)}(2)] 2 and [{PhN(H)Li}(4).(4-Bu-t-pyr)(6)] 3 has been synthesised by reacting the aromatic primary amide with two molar equivalents of the appropriate pyridine-based solvent (pyridine, 4-methylpyridine and 4-tert-butylpyridine, respectively) in hexane-toluene solution. X-Ray crystallographic studies have revealed three contrasting structures: 1 adopts a dinuclear, dimeric [(anilido)N-Li](2) ring arrangement with a transoid (anti) conformation of amido substituents; 2 adopts a similar arrangement but with a cisoid (syn) conformation of amido substituents; and 3 adopts a novel tetranuclear arrangement with a central [(anilido)N-Li](2) transoid ring, separating two mixed ligand [(anilido)N-Li-(pyr)N-Li] rings, made possible by the unusual mu-bonding of a 4-tert-butylpyridine ligand. A combination of H-1, Li-7 and C-13 NMR spectroscopic studies at 300 K suggests similar environments exist for corresponding atoms in [H-2(8)]-toluene solutions of 1, 2 or 3. Further examination of the solution of 3 over the temperature window (300-193 K) has detected a fluxional structure involving the intramolecular exchange of two distinct types of anilido ligand, consistent with those present in the molecular structure of crystalline 3.

KW - amide ladder structures

KW - crystal structures

KW - adducts

KW - dimers

U2 - 10.1039/B000576M

DO - 10.1039/B000576M

M3 - Article

VL - 7

SP - 1225

EP - 1231

JO - Journal of the Chemical Society, Dalton Transactions

T2 - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

SN - 0300-9246

ER -