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Spectroscopic Evidence for Intramolecular Mo VI (O 2 )····HO−C Hydrogen Bonding in Solution
Author(s) -
Glas Holger,
Spiegler Michael,
Thiel Werner R.
Publication year - 1998
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/(sici)1099-0682(199802)1998:2<275::aid-ejic275>3.0.co;2-h
Subject(s) - chemistry , intramolecular force , hydrogen bond , cyclohexanol , ligand (biochemistry) , kinetic resolution , denticity , pyridine , intermolecular force , crystallography , stereochemistry , polymer chemistry , medicinal chemistry , crystal structure , catalysis , molecule , enantioselective synthesis , organic chemistry , biochemistry , receptor
The ring‐opening reaction of epoxycyclohexane with 2‐[3(5)‐pyrazolyl]pyridine results in the formation of racemic trans ‐2‐[3‐(2‐pyridyl)‐1‐pyrazolyl]cyclohexanol ( 1 ). Kinetic resolution with lipase B from candida antarctica gives the (1 S ,2 S ) enantiomer of 1 , the solid‐state structure of which was determined by X‐ray crystallography, as an enantiomerically pure tridentate ligand. Investigation by NMR spectroscopy of the corresponding oxodiperoxomolybdenum complex 2 , where 1 acts as a bidentate chelate, proves the formation of a weak intramolecular Mo VI (O 2 )····HO−C bridge in CHCl 3 solution. This H bonding is broken by solvents such as acetone, THF or DMF, which are capable of forming hydrogen bonds to alcohols. Intermolecular hydrogen bonds between the OH groups and molybdenum peroxo moieties are also found in the solid‐state structure of 2 , leading to a helical arrangement of the peroxo complexes.