Ligand reactivities in platinum and palladium chalcogen complexes

Abstract

In this thesis we shall report on two metalloligands, [Pt2(B5-X)2(dppy)4] and [PtX4(P-P)] (X = S or Se; P-P = 2PPh3 or dppe) and their heterometallic aggregates. The high reactivity of d10 metal-metal bonded complexes towards {PtX4} and {Pt2(B5-S)2} core have been demonstrated through the successful isolation of a number of novel homo- and hetero-polynuclear complexes of [Pt2M2(N<3-S)2(N<-dppy)2(dppy)2(N<-dppm)][PF6]2, [Pd3Pt2(B53-X)2(N<-dppy)4(dppy)4][PF6]3; [PtM2(B53-X)2(P-P)(dppmSe-N:2Se,P4)2][PF6]2 (M= Pd or Pt). The optical limiting properties of the newly synthesized complexes are also reported.An extension of alkylation and oxidation of the {Pt2(B5-S)2} core will also be included. A series of imidazolium and thiazolium ligands have been successfully anchored on the core with further hetero-alkylation using Me2SO4. The dialkylated complexes were mixed with Pd(OAc)2 for Suzuki-Miyaura cross-coupling reactions, giving promising yields. It was also proved that in the presence of lanthanide(III)/scandium(III) salts or strong oxidants, the {Pt2(B5-S)2} core was easily oxidized to [Pt2(B52-S2O2H)(PPh3)4][PF6].