Lithiated amidines: syntheses and structural characterisations

J Barker, D Barr, N D R Barnett, W Clegg, I CraggHine, M G Davidson, R P Davies, S M Hodgson, J A K Howard, M Kilner, C W Lehmann, I LopezSolera, Robert Mulvey, P R Raithby, R Snaith

Research output: Contribution to journalArticle

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Abstract

The reaction of a toluene solution of PhNC(Ph)NHPh (N,N'-diphenylbenzamidine) with n-butyllithium gave the toluene-solvated amidinolithium compound {Li[PhNC(Ph)NPh]}(n) 1. Similarly the same reaction performed in the presence of the Lewis-base donors (Me(2)N)(3)PO (hmpa), Me(2)N(CH2)(2)NMe(2) (tmen) or [Me(2)N(CH2)(2)](2)NMe (pmdien) yielded the amidinolithium complexes {Li[PhNC(Ph)NPh . hmpa]}(2) 2, {Li[PhNC(Ph)NPh]. tmen} 3 and {Li[PhNC(Ph)NPh]. pmdien} 4 respectively. In addition the reaction of a toluene solution of the related amidine PhNC(Me)NHPh(N,N'-diphenylacetamidine) with LiBu(II) in the presence of hmpa afforded {Li[PhNC(Me)NPh]. hmpa}(2) 5. The solid-state structures of 2-5, which have been resolved by single-crystal X-ray diffraction methods, show both similarities and differences The complexes 3 and 4, which contain the di- and tri-dentate ligands tmen and pmdien respectively, are monomeric, whilst use of the unidentate Lewis base hmpa results in dimers 2 and 5. However, the way in which dimerisation is achieved differs. The co-ordination geometry about the lithium cation is clearly influenced by the choice of donor and as such shows how change in the denticity of the donor ligand utilised can have a significant effect on the solid-state structure of the system.

Original languageEnglish
Pages (from-to)951-955
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number6
DOIs
Publication statusPublished - 21 Mar 1997

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Amidines
Toluene
Lewis Bases
Ligands
Dimerization
Lithium
Dimers
Cations
Single crystals
X ray diffraction
Geometry

Keywords

  • crystal structures
  • complexes
  • lithiated amidines

Cite this

Barker, J., Barr, D., Barnett, N. D. R., Clegg, W., CraggHine, I., Davidson, M. G., ... Snaith, R. (1997). Lithiated amidines: syntheses and structural characterisations. Journal of the Chemical Society, Dalton Transactions, (6), 951-955. https://doi.org/10.1039/A605849C
Barker, J ; Barr, D ; Barnett, N D R ; Clegg, W ; CraggHine, I ; Davidson, M G ; Davies, R P ; Hodgson, S M ; Howard, J A K ; Kilner, M ; Lehmann, C W ; LopezSolera, I ; Mulvey, Robert ; Raithby, P R ; Snaith, R . / Lithiated amidines: syntheses and structural characterisations. In: Journal of the Chemical Society, Dalton Transactions. 1997 ; No. 6. pp. 951-955.
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abstract = "The reaction of a toluene solution of PhNC(Ph)NHPh (N,N'-diphenylbenzamidine) with n-butyllithium gave the toluene-solvated amidinolithium compound {Li[PhNC(Ph)NPh]}(n) 1. Similarly the same reaction performed in the presence of the Lewis-base donors (Me(2)N)(3)PO (hmpa), Me(2)N(CH2)(2)NMe(2) (tmen) or [Me(2)N(CH2)(2)](2)NMe (pmdien) yielded the amidinolithium complexes {Li[PhNC(Ph)NPh . hmpa]}(2) 2, {Li[PhNC(Ph)NPh]. tmen} 3 and {Li[PhNC(Ph)NPh]. pmdien} 4 respectively. In addition the reaction of a toluene solution of the related amidine PhNC(Me)NHPh(N,N'-diphenylacetamidine) with LiBu(II) in the presence of hmpa afforded {Li[PhNC(Me)NPh]. hmpa}(2) 5. The solid-state structures of 2-5, which have been resolved by single-crystal X-ray diffraction methods, show both similarities and differences The complexes 3 and 4, which contain the di- and tri-dentate ligands tmen and pmdien respectively, are monomeric, whilst use of the unidentate Lewis base hmpa results in dimers 2 and 5. However, the way in which dimerisation is achieved differs. The co-ordination geometry about the lithium cation is clearly influenced by the choice of donor and as such shows how change in the denticity of the donor ligand utilised can have a significant effect on the solid-state structure of the system.",
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Barker, J, Barr, D, Barnett, NDR, Clegg, W, CraggHine, I, Davidson, MG, Davies, RP, Hodgson, SM, Howard, JAK, Kilner, M, Lehmann, CW, LopezSolera, I, Mulvey, R, Raithby, PR & Snaith, R 1997, 'Lithiated amidines: syntheses and structural characterisations', Journal of the Chemical Society, Dalton Transactions, no. 6, pp. 951-955. https://doi.org/10.1039/A605849C

Lithiated amidines: syntheses and structural characterisations. / Barker, J ; Barr, D ; Barnett, N D R ; Clegg, W ; CraggHine, I ; Davidson, M G ; Davies, R P ; Hodgson, S M ; Howard, J A K ; Kilner, M ; Lehmann, C W ; LopezSolera, I ; Mulvey, Robert; Raithby, P R ; Snaith, R .

In: Journal of the Chemical Society, Dalton Transactions, No. 6, 21.03.1997, p. 951-955.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Lithiated amidines: syntheses and structural characterisations

AU - Barker, J

AU - Barr, D

AU - Barnett, N D R

AU - Clegg, W

AU - CraggHine, I

AU - Davidson, M G

AU - Davies, R P

AU - Hodgson, S M

AU - Howard, J A K

AU - Kilner, M

AU - Lehmann, C W

AU - LopezSolera, I

AU - Mulvey, Robert

AU - Raithby, P R

AU - Snaith, R

PY - 1997/3/21

Y1 - 1997/3/21

N2 - The reaction of a toluene solution of PhNC(Ph)NHPh (N,N'-diphenylbenzamidine) with n-butyllithium gave the toluene-solvated amidinolithium compound {Li[PhNC(Ph)NPh]}(n) 1. Similarly the same reaction performed in the presence of the Lewis-base donors (Me(2)N)(3)PO (hmpa), Me(2)N(CH2)(2)NMe(2) (tmen) or [Me(2)N(CH2)(2)](2)NMe (pmdien) yielded the amidinolithium complexes {Li[PhNC(Ph)NPh . hmpa]}(2) 2, {Li[PhNC(Ph)NPh]. tmen} 3 and {Li[PhNC(Ph)NPh]. pmdien} 4 respectively. In addition the reaction of a toluene solution of the related amidine PhNC(Me)NHPh(N,N'-diphenylacetamidine) with LiBu(II) in the presence of hmpa afforded {Li[PhNC(Me)NPh]. hmpa}(2) 5. The solid-state structures of 2-5, which have been resolved by single-crystal X-ray diffraction methods, show both similarities and differences The complexes 3 and 4, which contain the di- and tri-dentate ligands tmen and pmdien respectively, are monomeric, whilst use of the unidentate Lewis base hmpa results in dimers 2 and 5. However, the way in which dimerisation is achieved differs. The co-ordination geometry about the lithium cation is clearly influenced by the choice of donor and as such shows how change in the denticity of the donor ligand utilised can have a significant effect on the solid-state structure of the system.

AB - The reaction of a toluene solution of PhNC(Ph)NHPh (N,N'-diphenylbenzamidine) with n-butyllithium gave the toluene-solvated amidinolithium compound {Li[PhNC(Ph)NPh]}(n) 1. Similarly the same reaction performed in the presence of the Lewis-base donors (Me(2)N)(3)PO (hmpa), Me(2)N(CH2)(2)NMe(2) (tmen) or [Me(2)N(CH2)(2)](2)NMe (pmdien) yielded the amidinolithium complexes {Li[PhNC(Ph)NPh . hmpa]}(2) 2, {Li[PhNC(Ph)NPh]. tmen} 3 and {Li[PhNC(Ph)NPh]. pmdien} 4 respectively. In addition the reaction of a toluene solution of the related amidine PhNC(Me)NHPh(N,N'-diphenylacetamidine) with LiBu(II) in the presence of hmpa afforded {Li[PhNC(Me)NPh]. hmpa}(2) 5. The solid-state structures of 2-5, which have been resolved by single-crystal X-ray diffraction methods, show both similarities and differences The complexes 3 and 4, which contain the di- and tri-dentate ligands tmen and pmdien respectively, are monomeric, whilst use of the unidentate Lewis base hmpa results in dimers 2 and 5. However, the way in which dimerisation is achieved differs. The co-ordination geometry about the lithium cation is clearly influenced by the choice of donor and as such shows how change in the denticity of the donor ligand utilised can have a significant effect on the solid-state structure of the system.

KW - crystal structures

KW - complexes

KW - lithiated amidines

U2 - 10.1039/A605849C

DO - 10.1039/A605849C

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JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

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Barker J, Barr D, Barnett NDR, Clegg W, CraggHine I, Davidson MG et al. Lithiated amidines: syntheses and structural characterisations. Journal of the Chemical Society, Dalton Transactions. 1997 Mar 21;(6):951-955. https://doi.org/10.1039/A605849C