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Synthesis, X‐ray Crystallographic and 1 H NMR Spectroscopic Structural Studies on Cobalt( II ) Complexes of Homoscorpionate, Heteroscorpionates and Chiral Tris(pyrazolyl)borates Obtained from 5(3)‐ Iso propyl‐3(5)‐phenylpyrazole and 3,5‐Dimethylpyrazole
Author(s) -
Ruman Tomasz,
Ciunik Zbigniew,
Wołowiec Stanislaw
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300022
Subject(s) - isopropyl , chemistry , cobalt , tetrahydrofuran , toluene , sodium borohydride , crystallography , medicinal chemistry , inorganic chemistry , solvent , organic chemistry , catalysis
Condensation of 5(3)‐isopropyl‐3(5)‐phenylpyrazole with sodium borohydride led to a mixture of tris(pyrazolyl)borate ligands (Tp x ) − the homoscorpionate hydrotris(5‐isopropyl‐3‐phenylpyrazolyl)borate and the heteroscorpionates hydro(3‐isopropyl‐5‐phenylpyrazolyl)bis(5‐isopropyl‐3‐phenylpyrazolyl)borate and hydrobis(3‐isopropyl‐5‐phenylpyrazolyl)(5‐isopropyl‐3‐phenylpyrazolyl)borate − that were converted into Tp x Co(NCS) complexes. The molecular structures of pentacoordinate[hydrotris(5‐isopropyl‐3‐phenylpyrazolyl)borato](tetrahydrofuran)(thiocyanato)cobalt( II ) ( 1‐THF ) and [hydrobis(3‐isopropyl‐5‐phenylpyrazolyl)(5‐isopropyl‐3‐cobalt( II ) ( 3‐THF ) were elucidated crystallographically. Hydro(3,5‐dimethylpyrazolyl)bis(5‐isopropyl‐3‐phenylpyrazolyl)borate was also obtained by condensation of 2.1 equiv. of 5(3)‐isopropyl‐3(5)‐phenylpyrazole and 0.9 equiv. of 3,5‐dimethylpyrazole with sodium borohydride, and it was converted into [hydro(3,5‐dimethylpyrazolyl)bis(5‐isopropyl‐3‐phenylpyrazolyl)borato](thiocyanato)cobalt( II ) ( 4 ), which was characterized by X‐ray crystallography. The latter was converted thermally under mild conditions (358 K in toluene) into [hydro(3,5‐dimethylpyrazolyl)(3‐isopropyl‐5‐phenylpyrazolyl)(5‐isopropyl‐3‐phenylpyrazolyl)borato](thiocyanato)cobalt( II ) ( 9 ) in 45% yield, as was concluded from the 1 H NMR spectrum of the post‐reaction mixture. The dimer of 9 was obtained as single crystals from toluene/hexane and its structure was determined crystallographically. Two chiral Tp x ligands of opposite boron‐centered configurations are coordinated to cobalt( II ) ions in a κ 3 fashion. The pentacoordinate metal ions are bridged head‐to‐tail by the thiocyanate anions. This chiral Tp x ligand is the first example of a borate with fixed boron‐centered chirality. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)