The 1 : 1 co-crystallization of enantiomers of an arene-tethered and ortho-metallated N-heterocyclic carbene ruthenium(II) half-sandwich complex: Synthesis, structural characterization and theoretical study

KARABIYIK H., KILINÇARSLAN R., AYGÜN M., Cetinkaya B., Gardia-Granda S.

SOLID STATE SCIENCES, cilt.10, sa.1, ss.104-113, 2008 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 10 Sayı: 1
  • Basım Tarihi: 2008
  • Doi Numarası: 10.1016/j.solidstatesciences.2007.08.011
  • Dergi Adı: SOLID STATE SCIENCES
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.104-113
  • Anahtar Kelimeler: half-sandwich complex, ortho-metallation, ruthenacycle, co-crystallization, non-merohedral twin, DFT-B3LYP/LanL2DZ, asymmetric synthons, EFFECTIVE CORE POTENTIALS, MOLECULAR CALCULATIONS, CATALYTIC SYNTHESIS, PALLADIUM(II) COMPLEXES, ALKENE METATHESIS, STABLE CARBENES, C-C, LIGAND, 2,3-DIMETHYLFURAN, CYCLOISOMERIZATION
  • Dokuz Eylül Üniversitesi Adresli: Evet

Özet

The reaction of [RuCl2(p-cymene)](2) with in situ deprotonated NHC precursor 1,3-bis(biphenyl-2-yl)imidazolinium chloride was carried out in p-xylene at 140 degrees C to produce [RuCl(eta(1)-CN(eta(1)-C6H3Ph-1,2)N(eta(6)-C6H3Ph-2), 2, in which the NHC moiety acts as a tridentate C,C',C ''-ligand. The complex 2 was characterized by NMR spectroscopy and X-ray crystallographic study. Crystallographic analysis combined with computational study regarding the compound, 1-[eta(6) -(2'-biphenyl)]-3-[2-phenyl-1,2-phenylene]imidazolidin-2-ylidenechlororuthenium(II), 2, reveals that its metal-centered enantiomers are co-crystallized in 1: 1 ratio and NHC frame possessing a tridentate coordination mode consists of a-donation of the carbene carbon, eta(6)-arene tethering of terminal biaryl and eta(1)-coordination of the biphenyl ring at 2-position. Enantiomers of the complex are packed as asymmetric dimers in solid state formed by C-H center dot center dot center dot Cl type weak H-bonds and C-H center dot center dot center dot pi type interactions giving rise to asymmetric chains. Both interactions serve to stabilization of the extended structure. (c) 2007 Elsevier Masson SAS. All rights reserved.