title: Monoorganobismuth(III) dihalides containing the new pincer 2,6-{MeN(CH2CH2)2NCH2}2C6H3 ligand: solution NMR, vibrational and single-crystal X-ray studies.
abstract: The reaction of RLi [R = 2,6-{MeN(CH2CH2)2NCH2}2C6H3 ] with BiCl3 (1:1 molar ratio) afforded RBiCl2 (2). RBiBr2 (3) and RBiI2 (4) were obtained by halogen-exchange reactions from 2 . The organobismuth(III) dihalides containing the new steric demanding (N,C,N)-pincer ligand were characterized both in solution and solid state. The molecular structures of compounds were established by single-crystal X-ray diffraction. They all show a T-shaped CBiX(2) core, stabilized by two strong intramolecular N-->Bi interactions in trans positions to each other. The overall (N,C,N)BiX2 core exhibits a distorted square-pyramidal coordination geometry. The NMR studies provided evidences for the presence of internal nitrogen-bismuth coordination in solution too. DFT calculations were performed on the related species [2,6-(R(2)NCH(2))(2)C(6)H(3)]BiX(2) (R = H, Me; X = Cl, Br, I) in order to elucidate the bond nature and vibrational spectroscopic features of these compounds.
authors.affiliation: Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-Bolyai, RO-400028, Cluj-Napoca, Romania. cristi@chem.ubbcluj.ro.
authors.forename: Albert
authors.initials: A
authors.lastname: Soran
authors.forename: Hans J
authors.initials: HJ
authors.lastname: Breunig
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Arca
authors.forename: Cristian
authors.initials: C
authors.lastname: Silvestru
mesh_terms: D001729:Bismuth / Q000737:chemistry*; D018360:Crystallography, X-Ray / Q000379:methods*; D006219:Halogens / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D006219:Halogens; D008024:Ligands; D009942:Organometallic Compounds; D001729:Bismuth