A NEW CLASS OF MIXED AZA-THIOETHER CROWN-CONTAINING A 1,10-PHENANTHROLINE SUBUNIT

The new aza-thioether crowns [15]ane(phen N-2)S-3 and [19]ane(phen N-2 )S-4 have been synthesised. Their complexation with nickel(II) salts a fforded a range of octahedral complexes. The single crystal structures of [Ni{[15]ane(phen N-5)S-3)}(NCMe)][BF4](2), [NiCl{[15]ane(phen N-2) S-3}]BF4 . dmf(dmf = dimethylformamide) and [Nil{[15]ane(phen N-2)S-3} ][I-3] have been determined and confirm N2S3 donation of the aza-thioe ther crown in a folded conformation to Ni-II with the sixth co-ordinat ion site taken up by MeCN, Cl- and I- respectively. The complex [Ni2Cl 2{[19]ane(phen N-2)S-4}(2)][BF4](2) . 3MeNO(2) shows a dichloro-bridge d binuclear structure with the aza-thioether crown bound via only two S- and two N-donors, with two thioether S-donors unbound. A dichloro-b ridged binuclear structure was found also for [Ni2Cl2{[12]ane-(py N)S- 3}(2)][BF4](2) . 1.5MeNO(2). The redox properties of [Ni{[15]ane(phen N-2)S-3}(NCMe)][BF4](2) in MeCN have been examined.