A new, flexible n,n,n-tripodal facially capping ligand system: synthesis and structural characterization of beta-triketimines and their m(co)(3) complexes (m = cr, mo, w)

D. Barnes, G.L. Brown, M. Brownhill, I. German, C.J. Herbert, A. Jolleys, A.R. Kennedy, B. Liu

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Reaction of imidoyl chlorides Ar*N=CCIR (Ar* = 2-iPrC(6)H(4), 2,6-iPr(2)C(6)H(3), 2-MeOC6H4; R = Me, Ph, tBu) with [Li(nacnac)] [nacnac = (Ar*NCMe)(2)CH] gives beta-triketimines L, most of which exist in solution in equilibrium with their imine/enamine tautomers. The route is highly modular, allowing independent variation of at least five parameters. The solution equilibria are very sensitive to such substituent pattern variation. Single-crystal X-ray diffraction analyses of examples of both tautomers and a geometric isomer in the solid state are presented, alongside solution NMR studies of the tautomerism. All examples revert exclusively to the beta-triimine form on complexation with M(CO)(3) fragments (M = Cr, Mo, W). Facial isomers result. The ligands are weak sigma-donors, as adjudged by CO IR stretching frequencies in [LM(CO)(3)], Crystal-structure determination on the isostructural pair [HC(2-iPrC(6)H(4)N=CMe)(3)M(CO)(3)] (M = Cr, Mo) revealed a hexagonal packing arrangement composed of aryl-aryl and carbonyl (CO)-H-C interactions which generates pseudocylindrical voids accounting for 6-9 % of the crystal volume. In only one case were these occupied by solvent molecules, This family of facially capping N,N,N-ligands with finely tunable bulk have wide potential in coordination chemistry.
LanguageEnglish
Pages1219-1233
Number of pages14
JournalEuropean Journal of Inorganic Chemistry
Issue number9
DOIs
Publication statusPublished - Mar 2009

Fingerprint

Ligands
Isomers
Imines
Complexation
Stretching
Chlorides
Crystal structure
Nuclear magnetic resonance
Single crystals
X ray diffraction
Crystals
Molecules

Keywords

  • tridentate ligands
  • N ligands
  • ligand design
  • chromium
  • microporous materials
  • coordination chemistry
  • carbonic-anhydrase
  • crystal-structure
  • metal-carbonyls
  • bond formation
  • site
  • polymerization
  • nickel(ii)
  • catalysis
  • ethylene

Cite this

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title = "A new, flexible n,n,n-tripodal facially capping ligand system: synthesis and structural characterization of beta-triketimines and their m(co)(3) complexes (m = cr, mo, w)",
abstract = "Reaction of imidoyl chlorides Ar*N=CCIR (Ar* = 2-iPrC(6)H(4), 2,6-iPr(2)C(6)H(3), 2-MeOC6H4; R = Me, Ph, tBu) with [Li(nacnac)] [nacnac = (Ar*NCMe)(2)CH] gives beta-triketimines L, most of which exist in solution in equilibrium with their imine/enamine tautomers. The route is highly modular, allowing independent variation of at least five parameters. The solution equilibria are very sensitive to such substituent pattern variation. Single-crystal X-ray diffraction analyses of examples of both tautomers and a geometric isomer in the solid state are presented, alongside solution NMR studies of the tautomerism. All examples revert exclusively to the beta-triimine form on complexation with M(CO)(3) fragments (M = Cr, Mo, W). Facial isomers result. The ligands are weak sigma-donors, as adjudged by CO IR stretching frequencies in [LM(CO)(3)], Crystal-structure determination on the isostructural pair [HC(2-iPrC(6)H(4)N=CMe)(3)M(CO)(3)] (M = Cr, Mo) revealed a hexagonal packing arrangement composed of aryl-aryl and carbonyl (CO)-H-C interactions which generates pseudocylindrical voids accounting for 6-9 {\%} of the crystal volume. In only one case were these occupied by solvent molecules, This family of facially capping N,N,N-ligands with finely tunable bulk have wide potential in coordination chemistry.",
keywords = "tridentate ligands, N ligands, ligand design, chromium, microporous materials, coordination chemistry, carbonic-anhydrase, crystal-structure, metal-carbonyls, bond formation, site, polymerization, nickel(ii), catalysis, ethylene",
author = "D. Barnes and G.L. Brown and M. Brownhill and I. German and C.J. Herbert and A. Jolleys and A.R. Kennedy and B. Liu",
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year = "2009",
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A new, flexible n,n,n-tripodal facially capping ligand system: synthesis and structural characterization of beta-triketimines and their m(co)(3) complexes (m = cr, mo, w). / Barnes, D.; Brown, G.L.; Brownhill, M.; German, I.; Herbert, C.J.; Jolleys, A.; Kennedy, A.R.; Liu, B.

In: European Journal of Inorganic Chemistry, No. 9, 03.2009, p. 1219-1233.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A new, flexible n,n,n-tripodal facially capping ligand system: synthesis and structural characterization of beta-triketimines and their m(co)(3) complexes (m = cr, mo, w)

AU - Barnes, D.

AU - Brown, G.L.

AU - Brownhill, M.

AU - German, I.

AU - Herbert, C.J.

AU - Jolleys, A.

AU - Kennedy, A.R.

AU - Liu, B.

N1 - Strathprints' policy is to record up to 8 authors per publication, plus any additional authors based at the University of Strathclyde. More authors may be listed on the official publication than appear in the Strathprints' record.

PY - 2009/3

Y1 - 2009/3

N2 - Reaction of imidoyl chlorides Ar*N=CCIR (Ar* = 2-iPrC(6)H(4), 2,6-iPr(2)C(6)H(3), 2-MeOC6H4; R = Me, Ph, tBu) with [Li(nacnac)] [nacnac = (Ar*NCMe)(2)CH] gives beta-triketimines L, most of which exist in solution in equilibrium with their imine/enamine tautomers. The route is highly modular, allowing independent variation of at least five parameters. The solution equilibria are very sensitive to such substituent pattern variation. Single-crystal X-ray diffraction analyses of examples of both tautomers and a geometric isomer in the solid state are presented, alongside solution NMR studies of the tautomerism. All examples revert exclusively to the beta-triimine form on complexation with M(CO)(3) fragments (M = Cr, Mo, W). Facial isomers result. The ligands are weak sigma-donors, as adjudged by CO IR stretching frequencies in [LM(CO)(3)], Crystal-structure determination on the isostructural pair [HC(2-iPrC(6)H(4)N=CMe)(3)M(CO)(3)] (M = Cr, Mo) revealed a hexagonal packing arrangement composed of aryl-aryl and carbonyl (CO)-H-C interactions which generates pseudocylindrical voids accounting for 6-9 % of the crystal volume. In only one case were these occupied by solvent molecules, This family of facially capping N,N,N-ligands with finely tunable bulk have wide potential in coordination chemistry.

AB - Reaction of imidoyl chlorides Ar*N=CCIR (Ar* = 2-iPrC(6)H(4), 2,6-iPr(2)C(6)H(3), 2-MeOC6H4; R = Me, Ph, tBu) with [Li(nacnac)] [nacnac = (Ar*NCMe)(2)CH] gives beta-triketimines L, most of which exist in solution in equilibrium with their imine/enamine tautomers. The route is highly modular, allowing independent variation of at least five parameters. The solution equilibria are very sensitive to such substituent pattern variation. Single-crystal X-ray diffraction analyses of examples of both tautomers and a geometric isomer in the solid state are presented, alongside solution NMR studies of the tautomerism. All examples revert exclusively to the beta-triimine form on complexation with M(CO)(3) fragments (M = Cr, Mo, W). Facial isomers result. The ligands are weak sigma-donors, as adjudged by CO IR stretching frequencies in [LM(CO)(3)], Crystal-structure determination on the isostructural pair [HC(2-iPrC(6)H(4)N=CMe)(3)M(CO)(3)] (M = Cr, Mo) revealed a hexagonal packing arrangement composed of aryl-aryl and carbonyl (CO)-H-C interactions which generates pseudocylindrical voids accounting for 6-9 % of the crystal volume. In only one case were these occupied by solvent molecules, This family of facially capping N,N,N-ligands with finely tunable bulk have wide potential in coordination chemistry.

KW - tridentate ligands

KW - N ligands

KW - ligand design

KW - chromium

KW - microporous materials

KW - coordination chemistry

KW - carbonic-anhydrase

KW - crystal-structure

KW - metal-carbonyls

KW - bond formation

KW - site

KW - polymerization

KW - nickel(ii)

KW - catalysis

KW - ethylene

UR - http://dx.doi.org/10.1002/ejic.200801022

U2 - 10.1002/ejic.200801022

DO - 10.1002/ejic.200801022

M3 - Article

SP - 1219

EP - 1233

JO - European Journal of Inorganic Chemistry

T2 - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 9

ER -