Synthesis and spectroscopy of mono- and di-nuclear copper complexes of a pyrazolylcyclotriphosphazene. Crystal structure of an unusual cyclotriphosphazene-bridged dicopper complex

Abstract

The mononuclear copper(II) complexes [CuL(ClO₄)(H₂O)₂]ClO₄ and [CuL(bipy)(ClO₄)]ClO₄[L = 2,2,4,4,6,6-hexakis(3,5-dimethylpyrazolyl)-2λ⁵,4λ⁵,6λ⁵-cyclotriphosphaza-1,3,5-triene] have been prepared and characterized by optical, EPR and IR spectral data. The crystal structure of an unusual cyclophosphazene-bridged dicopper complex [H₂dmpz][(CuCl₂)₂{N₃P₃O(dmpz)₅}](Hdmpz = 3,5-dimethylpyrazole) has been determined: space group P, a= 11.640(3), b= 14.497(14), c= 14.775(3), α= 77.62(6), β= 82.10(2), γ= 74.88(6)°, and Z= 2. The geometry around both copper atoms is a distorted trigonal bipyramidal with the axial positions occupied by pyrazolyl pyridinic nitrogens and the equatorial positions by one cyclophosphazene ring nitrogen and two chlorine atoms.