The electronic properties and stereochemistry of the copper(II) ion. Part VI. Bis(bipyridyl)copper(II) complexes

Abstract

The electronic, e.s.r., and i.r. spectra of a series of [Cu bipy₂X]Y-type complexes, where X = ONO^–, HCO₂^–, MeCO₂^–, PhCO₂^–, NCS^–, ½C₂O₄^2– and Y = ClO₄; where X = Y = ClO₄^–, NO₃^–, and BF₄^–; and [Cu bipy₂NH₃]X₂, where X = ClO₄^– and BF₄^–, are reported. By comparing these electronic properties with those of the trigonal-bipyramidal [Cu bipy₂l]I and the cis-distorted octahedral [Cu bipy₂(ONO)]NO₃ complexes, possible molecular structures are suggested. The complexes with X = ONO^– or a carboxylate anion have a cis-distorted octahedral stereochemistry; with X = NCS^– or NH₃ and approximately trigonal-bipyramidal stereochemistry is suggested. Possible stereochemistries for the complexes Cu bipy₂X₂, where X = ClO₄^–, BF₄^–, and NO₃^–, are discussed.

The molecular structures of the corresponding [Cu phen₂X]Y type complexes are considered to be analogous.