Aggregation patterns in alpha, alpha' stabilized carbocations: Assemley of a sodium cage polymer by slip-stacking of dimers

K.W. Henderson, A.R. Kennedy, D.J. McDougall

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The ,'-stabilized carbanion complexes [PhSO2CHCNNa·THF], 3, [t-BuSO2CHCNNa], 4, [PhSO2CHCNK], 5, [t-BuSO2CHCNK], 6, and [MeSO2CHCNLi·TMEDA], 7, have been synthesized via the metalation of the parent (organo)sulfonylacetonitriles by BuLi, BuNa, or BnK in THF solution (or THF/TMEDA in the case of 7). In addition, complexes 3 and 7 have been characterized by single-crystal X-ray analyses and have been found to adopt related structures in the solid state. Complex 7 is a molecular dimer containing a central 12-membered (OSCCNLi)2 ring core, with each metal rendered tetracoordinate by binding to a chelating TMEDA molecule. As found in related complexes, no direct carbanion to lithium contacts are present in the structure of 7. Complex 3 forms a polymeric cage structure composed of associated 'dimeric' (OSCCNNa)2 rings, similar to those found in 7. The larger sodium cations, and the presence of only one THF molecule/metal, allow additional contacts with the anions, leading to hexacoordination at the metal centers. These contacts include long-range transannular Na-N interactions (2.8042(14) î..) across the central dimeric ring and 'interdimer' Na-C connections (2.8718(15) î..). Dissolution of complexes 3-6 and their lithiated derivatives [PhSO2CHCNLi·TMEDA], 1, and [t-BuSO2CHCNLi·THF], 2, in DMSO-d6 results in almost identical chemical shifts for each type of ligand. This suggests that charge-separated complexes of the form [RSO2CHCN]-[M(DMSO-d6)n]+ are formed in highly polar solution
Original languageEnglish
Pages (from-to)2736-2741
Number of pages5
JournalInorganic Chemistry
Volume42
Issue number8
DOIs
Publication statusPublished - 26 Mar 2003

Fingerprint

Dimers
Polymers
slip
Agglomeration
Metals
Sodium
dimers
sodium
Dimethyl Sulfoxide
Buna (trademark)
rings
polymers
metals
Molecules
Chemical shift
Chelation
Lithium
Anions
chemical equilibrium
Cations

Keywords

  • stabilized carbanion complexes
  • metalation of the parent
  • tetracoordinate
  • polymeric cage structure
  • polar solution

Cite this

@article{1a425aa0f31e4990887a24e1552aeb96,
title = "Aggregation patterns in alpha, alpha' stabilized carbocations: Assemley of a sodium cage polymer by slip-stacking of dimers",
abstract = "The ,'-stabilized carbanion complexes [PhSO2CHCNNa·THF], 3, [t-BuSO2CHCNNa], 4, [PhSO2CHCNK], 5, [t-BuSO2CHCNK], 6, and [MeSO2CHCNLi·TMEDA], 7, have been synthesized via the metalation of the parent (organo)sulfonylacetonitriles by BuLi, BuNa, or BnK in THF solution (or THF/TMEDA in the case of 7). In addition, complexes 3 and 7 have been characterized by single-crystal X-ray analyses and have been found to adopt related structures in the solid state. Complex 7 is a molecular dimer containing a central 12-membered (OSCCNLi)2 ring core, with each metal rendered tetracoordinate by binding to a chelating TMEDA molecule. As found in related complexes, no direct carbanion to lithium contacts are present in the structure of 7. Complex 3 forms a polymeric cage structure composed of associated 'dimeric' (OSCCNNa)2 rings, similar to those found in 7. The larger sodium cations, and the presence of only one THF molecule/metal, allow additional contacts with the anions, leading to hexacoordination at the metal centers. These contacts include long-range transannular Na-N interactions (2.8042(14) {\^i}..) across the central dimeric ring and 'interdimer' Na-C connections (2.8718(15) {\^i}..). Dissolution of complexes 3-6 and their lithiated derivatives [PhSO2CHCNLi·TMEDA], 1, and [t-BuSO2CHCNLi·THF], 2, in DMSO-d6 results in almost identical chemical shifts for each type of ligand. This suggests that charge-separated complexes of the form [RSO2CHCN]-[M(DMSO-d6)n]+ are formed in highly polar solution",
keywords = "stabilized carbanion complexes, metalation of the parent, tetracoordinate, polymeric cage structure, polar solution",
author = "K.W. Henderson and A.R. Kennedy and D.J. McDougall",
year = "2003",
month = "3",
day = "26",
doi = "10.1021/ic026194w",
language = "English",
volume = "42",
pages = "2736--2741",
journal = "Inorganic Chemistry",
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Aggregation patterns in alpha, alpha' stabilized carbocations: Assemley of a sodium cage polymer by slip-stacking of dimers. / Henderson, K.W.; Kennedy, A.R.; McDougall, D.J.

In: Inorganic Chemistry, Vol. 42, No. 8, 26.03.2003, p. 2736-2741.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Aggregation patterns in alpha, alpha' stabilized carbocations: Assemley of a sodium cage polymer by slip-stacking of dimers

AU - Henderson, K.W.

AU - Kennedy, A.R.

AU - McDougall, D.J.

PY - 2003/3/26

Y1 - 2003/3/26

N2 - The ,'-stabilized carbanion complexes [PhSO2CHCNNa·THF], 3, [t-BuSO2CHCNNa], 4, [PhSO2CHCNK], 5, [t-BuSO2CHCNK], 6, and [MeSO2CHCNLi·TMEDA], 7, have been synthesized via the metalation of the parent (organo)sulfonylacetonitriles by BuLi, BuNa, or BnK in THF solution (or THF/TMEDA in the case of 7). In addition, complexes 3 and 7 have been characterized by single-crystal X-ray analyses and have been found to adopt related structures in the solid state. Complex 7 is a molecular dimer containing a central 12-membered (OSCCNLi)2 ring core, with each metal rendered tetracoordinate by binding to a chelating TMEDA molecule. As found in related complexes, no direct carbanion to lithium contacts are present in the structure of 7. Complex 3 forms a polymeric cage structure composed of associated 'dimeric' (OSCCNNa)2 rings, similar to those found in 7. The larger sodium cations, and the presence of only one THF molecule/metal, allow additional contacts with the anions, leading to hexacoordination at the metal centers. These contacts include long-range transannular Na-N interactions (2.8042(14) î..) across the central dimeric ring and 'interdimer' Na-C connections (2.8718(15) î..). Dissolution of complexes 3-6 and their lithiated derivatives [PhSO2CHCNLi·TMEDA], 1, and [t-BuSO2CHCNLi·THF], 2, in DMSO-d6 results in almost identical chemical shifts for each type of ligand. This suggests that charge-separated complexes of the form [RSO2CHCN]-[M(DMSO-d6)n]+ are formed in highly polar solution

AB - The ,'-stabilized carbanion complexes [PhSO2CHCNNa·THF], 3, [t-BuSO2CHCNNa], 4, [PhSO2CHCNK], 5, [t-BuSO2CHCNK], 6, and [MeSO2CHCNLi·TMEDA], 7, have been synthesized via the metalation of the parent (organo)sulfonylacetonitriles by BuLi, BuNa, or BnK in THF solution (or THF/TMEDA in the case of 7). In addition, complexes 3 and 7 have been characterized by single-crystal X-ray analyses and have been found to adopt related structures in the solid state. Complex 7 is a molecular dimer containing a central 12-membered (OSCCNLi)2 ring core, with each metal rendered tetracoordinate by binding to a chelating TMEDA molecule. As found in related complexes, no direct carbanion to lithium contacts are present in the structure of 7. Complex 3 forms a polymeric cage structure composed of associated 'dimeric' (OSCCNNa)2 rings, similar to those found in 7. The larger sodium cations, and the presence of only one THF molecule/metal, allow additional contacts with the anions, leading to hexacoordination at the metal centers. These contacts include long-range transannular Na-N interactions (2.8042(14) î..) across the central dimeric ring and 'interdimer' Na-C connections (2.8718(15) î..). Dissolution of complexes 3-6 and their lithiated derivatives [PhSO2CHCNLi·TMEDA], 1, and [t-BuSO2CHCNLi·THF], 2, in DMSO-d6 results in almost identical chemical shifts for each type of ligand. This suggests that charge-separated complexes of the form [RSO2CHCN]-[M(DMSO-d6)n]+ are formed in highly polar solution

KW - stabilized carbanion complexes

KW - metalation of the parent

KW - tetracoordinate

KW - polymeric cage structure

KW - polar solution

UR - http://dx.doi.org/10.1021/ic026194w

U2 - 10.1021/ic026194w

DO - 10.1021/ic026194w

M3 - Article

VL - 42

SP - 2736

EP - 2741

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -