The ring-stacking principle in organolithium chemistry: its development through the isolation and crystal structures of hexameric iminolithium clusters (RR'C=NLi)6 (R'=Ph, R=But or Me2N; R=R'=Me2N or But)

D R ARMSTRONG, D BARR, R SNAITH, W CLEGG, Robert Mulvey, K WADE, D REED

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Abstract

Synthetic and X-ray crystallographic studies on two new iminolithium compounds, [But(Ph)CNLi]6(1) and [Me2N(Ph)CNLi]6(2), have revealed, in conjunction with previously reported work on [(Me2N)2CNLi]6(3) and (But2CNLi)6(4), a family of hexameric iminolithium species. All four compounds have remarkably similar solid-state structures based on slightly folded chair-shaped Li6 cores, the six smaller (isosceles) Li3 triangular faces of which are bridged by three-electron imino ligands through electron-deficient bonds. The precise determination of the structures of (1) and (2) has revealed features which were not apparent in the earlier limited and less fully refined structural studies on (3) and (4). Recognition of such features and their detailed analysis leads to a ring-stacking principle which envisages the formation of these hexameric structures from two slightly puckered trimeric rings, (RR′CNLi)3, brought together in a staggered arrangement. Extension of this principle allows the rationalisation of many other structures in lithium chemistry and facilitates structural predictions.
LanguageEnglish
Pages1071-1081
Number of pages11
JournalJournal of the Chemical Society, Dalton Transactions
Issue number5
DOIs
Publication statusPublished - May 1987

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Crystal structure
Electrons
Lithium
Ligands
X rays

Keywords

  • inorganic compounds
  • crystalline structures

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title = "The ring-stacking principle in organolithium chemistry: its development through the isolation and crystal structures of hexameric iminolithium clusters (RR'C=NLi)6 (R'=Ph, R=But or Me2N; R=R'=Me2N or But)",
abstract = "Synthetic and X-ray crystallographic studies on two new iminolithium compounds, [But(Ph)CNLi]6(1) and [Me2N(Ph)CNLi]6(2), have revealed, in conjunction with previously reported work on [(Me2N)2CNLi]6(3) and (But2CNLi)6(4), a family of hexameric iminolithium species. All four compounds have remarkably similar solid-state structures based on slightly folded chair-shaped Li6 cores, the six smaller (isosceles) Li3 triangular faces of which are bridged by three-electron imino ligands through electron-deficient bonds. The precise determination of the structures of (1) and (2) has revealed features which were not apparent in the earlier limited and less fully refined structural studies on (3) and (4). Recognition of such features and their detailed analysis leads to a ring-stacking principle which envisages the formation of these hexameric structures from two slightly puckered trimeric rings, (RR′CNLi)3, brought together in a staggered arrangement. Extension of this principle allows the rationalisation of many other structures in lithium chemistry and facilitates structural predictions.",
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author = "ARMSTRONG, {D R} and D BARR and R SNAITH and W CLEGG and Robert Mulvey and K WADE and D REED",
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T1 - The ring-stacking principle in organolithium chemistry: its development through the isolation and crystal structures of hexameric iminolithium clusters (RR'C=NLi)6 (R'=Ph, R=But or Me2N; R=R'=Me2N or But)

AU - ARMSTRONG, D R

AU - BARR, D

AU - SNAITH, R

AU - CLEGG, W

AU - Mulvey, Robert

AU - WADE, K

AU - REED, D

PY - 1987/5

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N2 - Synthetic and X-ray crystallographic studies on two new iminolithium compounds, [But(Ph)CNLi]6(1) and [Me2N(Ph)CNLi]6(2), have revealed, in conjunction with previously reported work on [(Me2N)2CNLi]6(3) and (But2CNLi)6(4), a family of hexameric iminolithium species. All four compounds have remarkably similar solid-state structures based on slightly folded chair-shaped Li6 cores, the six smaller (isosceles) Li3 triangular faces of which are bridged by three-electron imino ligands through electron-deficient bonds. The precise determination of the structures of (1) and (2) has revealed features which were not apparent in the earlier limited and less fully refined structural studies on (3) and (4). Recognition of such features and their detailed analysis leads to a ring-stacking principle which envisages the formation of these hexameric structures from two slightly puckered trimeric rings, (RR′CNLi)3, brought together in a staggered arrangement. Extension of this principle allows the rationalisation of many other structures in lithium chemistry and facilitates structural predictions.

AB - Synthetic and X-ray crystallographic studies on two new iminolithium compounds, [But(Ph)CNLi]6(1) and [Me2N(Ph)CNLi]6(2), have revealed, in conjunction with previously reported work on [(Me2N)2CNLi]6(3) and (But2CNLi)6(4), a family of hexameric iminolithium species. All four compounds have remarkably similar solid-state structures based on slightly folded chair-shaped Li6 cores, the six smaller (isosceles) Li3 triangular faces of which are bridged by three-electron imino ligands through electron-deficient bonds. The precise determination of the structures of (1) and (2) has revealed features which were not apparent in the earlier limited and less fully refined structural studies on (3) and (4). Recognition of such features and their detailed analysis leads to a ring-stacking principle which envisages the formation of these hexameric structures from two slightly puckered trimeric rings, (RR′CNLi)3, brought together in a staggered arrangement. Extension of this principle allows the rationalisation of many other structures in lithium chemistry and facilitates structural predictions.

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