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Synthesis and Characterization of an Open and a Cyclic Polyaza Complexes of Copper( II ) Having Caged Moiety; Cyclization Through Copper( II ) Enhanced Hydrolysis from Nitrile to Amide
Author(s) -
Park Min Jeong,
Seo Min Ji,
Chung Minchul,
Kwak CheeHun
Publication year - 2017
Publication title -
bulletin of the korean chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.237
H-Index - 59
ISSN - 1229-5949
DOI - 10.1002/bkcs.11303
Subject(s) - chemistry , moiety , acetonitrile , nitrile , ligand (biochemistry) , amide , copper , polymer chemistry , hydrolysis , electrophile , photochemistry , stereochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry , receptor
The preparation, X‐ray structure and properties of noncyclic ( 1 ) and cyclic ( 2 ) polyaza copper(II) complexes with caged moiety, and copper(II) enhanced hydrolysis of acetonitrile participated in the cyclization of 1 to 2 are reported. The average Cu‐N distances of complex 1 and 2 are somewhat shorter than those of square‐planar or square‐pyramidal complexes of analogue [14]‐membered ring copper(II) complexes. These results derived from the squeeze effect of caged moiety of bicyclononan. Reaction of formaldehyde and complex 1 in the presence of base in acetonitrile solution produced complex 2 . In this catalytic route, coordination of acetonitrile onto Cu(II) ion, a Lewis acid, of complex 1 makes the electrophilicity of the carbon of nitrile increased. Absorption maximum of the complex 2 is shifted to somewhat shorter wavelength than that of the complex 1 . It is supposed to the higher ligand field stabilization energy of complex 2 , which has cyclized ligand, comparing that of the complex 1 , which has open ligand. These complexes are stable against disproportionation in copper(I) state.