Copper distorted tetrahedral species

In the copper (II) azido-system the distorted tetrahedral species [CuN3]+, [Cu(N3)2], [Cu(N3)3] and [Cu(N3)4]2 are found in AN and TMP. In DMSO the stabilities of the anionic complexes are lower and [Cu(N3)3] has been found to be unstable in this solvent27. Autocomplex formation of copper(II) azide seems to occur in anhydrous dimethyl sulphoxide. 

Using 1,4,8,11-tetraazacyclotetradecane, the structure of complex (800) (distorted trigonal planar Cu-Cu 6.739 A) was determined. Reactivity with 02 was investigated to demonstrate the formation of trans-l,2-peroxo species.585 As part of their work with copper(I) complexes with 02, the structure of a dicopper(I) complex ((801) distorted tetrahedral 7.04 A), supported by macrocyclic ligand environment, was reported by Comba and co-workers. Tolman and co-workers structurally characterized a three-coordinate copper(I)-phenoxide complex (802) (planar T-shaped) that models the reduced form of GO.587 The copper(I) analogue [Cu(L)][CF3-SO3]-0.43MeOI I (803) of a copper(II) complex (534) was also reported to demonstrate the role of ligand framework conformability in CV /Cu1 redox potentials.434 Wilson and co-workers... 

Both copper(n) complexes 23(42+ and 23 ysy2"1" have electronic spectra typical of 4-coordinate and 5-coordinate species, respectively, in accordance with previously reported complexes possessing analogous ligand sets)99,1001 The same interconversion process can also be monitored by EPR,198 1011 and it was demonstrated in an unambiguous fashion that 23(42+ is a distorted tetrahedral complex and that the product of the changeover, 23 s2+, is a square pyramidal compound. 

The phosphine coordinated copper(I) thiophenolate [Cu3(SPh)3(PPh3)4] (28) has an analogous trimeric structure to those species with intramolecular coordination. although in this case the fourth extra phosphine ligand results in a distorted tetrahedral coordination of one of the copper atoms and a distortion of the Cu,S3 six-mcmbered heterocycle (Fig. 5). 

In the copper(II) system chloride and azide ligands lead to the same coordination types namely [CuX]+, [CUX2], [CuX3] and [CUX4], which seem to have distorted tetrahedral structures. Both in the manganese(II)-chloro and in the manganese(II) azido systems hexacoordinated species have been found 7 . 

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