Syntheses and studies on transition metal complexes involving phosphine and thioether ligands

A series of bi- and tetra-dentate, acyclic and macrocyclic, ligands containing phosphine and/or thioether donors and their transition metal complexes are described.A series of complexes has been prepared with primary or, secondary phosphine ligands with a view to these being used as precursors for the template synthesis of macrocycles. Cu1, Ag1 and Au1 complexes with PhHP(CH2)nPHPh (n = 2,3) have been characterised and in the case of the Cu1 complexes, ring closure reactions to form the P4 donor macrocyclic complex attempted. Also synthesised are the Moo and Wo and IR spectroscopies, together with single crystal X-ray studies, have shown that the fac-isomers are formed exclusively.Attempts to synthesise Ph2[14]- and Ph2[16]-aneP2N2, have been performed via both high dilution and metal template mediated techniques. Though final products have not been fully characterised there is some evidence for the macrocyclic species being present. All of the intermediates have been fully characterised.Reaction of the PtII complexes [Pt(L')][PF6]2 (L' = [12]-, [14]- and [16]aneS4) with X2 (X = Cl, Br) has given the unusual cationic PtIV species, [PtX2(L')][PF6]2. 195Pt NMR spectroscopic studies have confirmed the S4X2 donor set. These studies indicate cis-dihalides for [PtX2[12]aneS4][PF6]2 and [PtX2([14]aneS4][PF6]2, and trans-dihalides for [PtX2([16]aneS4][PF6]2. EXAFS studies on these complexes show that oxidation of PtII to PtIV typically results in a slight lengthening of the Pt-S bond.