A new class of mixed aza–thioether crown containing a 1,10-phenanthroline sub-unit
Abstract
The new aza–thioether crowns [15]ane(phen N2)S3 and [19]ane(phen N2)S4 have been synthesised. Their complexation with nickel(II) salts afforded a range of octahedral complexes. The single crystal structures of [Ni{[15]ane(phen N2)S3}(NCMe)][BF4]2, [NiCl{[15]ane(phen N2)S3}]BF4·dmf (dmf = dimethylformamide) and [NiI{[15]ane(phen N2)S3}][I3] have been determined and confirm N2S3 donation of the aza–thioether crown in a folded conformation to NiII with the sixth co-ordination site taken up by MeCN, Cl– and I– respectively. The complex [Ni2Cl2{[19]ane(phen N2)S4}2][BF4]2·3MeNO2 shows a dichlorobridged binuclear structure with the aza–thioether crown bound via only two S- and two N-donors, with two thioether S-donors unbound. A dichloro-bridged binuclear structure was found also for [Ni2Cl2{[12]ane(py N)S3}2][BF4]2·1.5MeNO2. The redox properties of [Ni{[15]ane(phen N2)S3}(NCMe)][BF4]2 in MeCN have been examined.