The preparation of new multimetallic materials and the functionalisation of nanoparticles with transition metal units

Saira Naeem, Engineering And Physical Sciences Research Council, Tom Welton, James Wilton-Ely
2014
A range of functionalised dithiocarbamates have been prepared and shown to successfully coordinate to a series of transition metal complexes which can then be used as a starting point for further chemistry. The potential to change the physical properties of these dithiocarbamate (DTC) complexes as a whole has been exploited through protonation of amine-terminated compounds. As well as rendering the complexes moderately soluble in water, the protonated terminal amine groups on the pendant arms
more » ... the pendant arms can serve as protecting groups for acid-sensitive co-ligands from cleavage or unwanted reaction during transformations in the presence of acids. An array of diallyl- and methylallyl-terminated DTC complexes have also been formed. The successful ring-closing metathesis of the diallyl units again demonstrates that the additional centre of reactivity on the pendent arms of the DTC ligand can be utilised, allowing further transformations to be carried out without affecting the rest of the complex. Furthermore, the methodology has been extended to nanoparticles where diallyl DTC units have been shown to stabilise the surface of gold nanoparticles. The study was also expanded to include dithiocarboxylate ligands. Few dithiocarboxylate complexes are known in literature, thus a comparison with the analogous dithiocarbamate species is provided in this report. The first examples of gold(I) complexes of this class of ligand (derived from N-heterocyclic carbenes) have been prepared. The synthesis and characterisation of ruthenium-alkenyl complexes bearing this ligand have also been presented and evidence of a remarkable rearrangement caused by their steric effect has been demonstrated. In addition, it has been shown that imidazolium-2-dithiocarboxylate betaines can be used to form monolayers on the surface of gold nanoparticles. The synthesis and characterisation of the first ruthenium vinyl complexes bearing the related dialkyldithiophosphate ligand, [S2P(OR)2]- are reported here. The resulting compounds demonstrate reactivity which di [...]
doi:10.25560/14608 fatcat:begiwbwvb5bbxd4b73hzqjgdzq