Copper(I) complexes of very bulky phosphines and development of new asymmetric thiatriazinyls for molecular magnets

Abstract

The coordination of copper(I) halides by bulky triarylphosphines DippPh2P and Dipp2PhP (Dipp=2,6-diisopropylphenyl), and the synthesis of a stable radical dimer of 3-trichloromethyl-5- (2-pyridyl)-1-thia-2,4,6-triazinyl are described in this thesis. Copper(I) with DippPh2P forms either trigonal-planar mononuclear [CuX(DippPh2P)2], or dinuclear dimeric [CuX(DippPh2P)]2 complexes (X = Cl, Br) depending on solvent; Dipp2PhP afforded [CuX(Dipp2PhP)]2 irrespective of stoichiometry.

On the thiatriazinyl radical synthesis, free-base 2-pyridyl- and 2-pyrimidylamidines were synthesized and used to prepare N'-(2,2,2-trichloroethanimidoyl)-pyrid-2-yl-carboximidamide and N'-(2,2,2-trichloroethanimidoyl)-pyrimid-2-yl-carboximidamide. Condensation of HCl salts of the former with S2Cl2 or (better) SCl2 formed the required 1-chloro-3-trichloromethyl-5-(2-pyridyl)-1-thia-2,4,6-triazine, but the preparation was inhibited by full or partial protonation at the 2-pyridyl N atom. Removal of HCl under pyrolysis conditions has been partly successful and allowed for the preparation of a first sample of the target 3-trichloromethyl-5-(2-pyridyl)-1-thia-2,4,6-triazinyl radical dimer. The products reported have been fully characterized by chemical, spectroscopic and single-crystal, X-ray diffraction.