Synthesis and electrical conductivity of a new family of Pt mixed valence complexes: Pt 6(NH 3) 14Cl 10X 4 (X=C10 4, BF 4 and PF 6)

Abstract

A new family of Pt mixed valence complexes : Pt 6(NH 3) 14Cl 10X 4 (X=C10 4, BF 4 and PF 6) was synthesized from the Magnus green salt (MGS) by the partial oxidation with an oxidant of H 2O 2 or by electrochemical method. On partial oxidation, the 1 6 of Cl − ligands in MGS are randomly replaced by NH 3 ligands and simultaneously counter ions X are introduced. These complexes comprise of one-dimensional chains with direct contact between Pt atoms and consequently a quasi-one-dimensional band made up of 5d z2 orbital of Pt is formed. The average valence of Pt is +2.33 and the distance between Pt atoms along a chain is shorter than or comparable to that of K 2[Pt(CN) 4]Br 0.3·xH 2O (KCP). The electrical conductivity σ and esr spectra of these complexes were presented.