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.
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