Multimetallic arrays: symmetrical bi-, tri- and tetrametallic complexes based on the group 10 metals and the functionalisation of gold nanoparticles with nickel-phosphine surface units

Edward R Knight; Nina H Leung; Yvonne H Lin; Andrew R Cowley; David J Watkin; Amber L Thompson; Graeme Hogarth; James D E T Wilton-Ely

doi:10.1039/b821947h

Multimetallic arrays: symmetrical bi-, tri- and tetrametallic complexes based on the group 10 metals and the functionalisation of gold nanoparticles with nickel-phosphine surface units

Dalton Trans. 2009 May 21:(19):3688-97. doi: 10.1039/b821947h. Epub 2009 Mar 13.

Authors

Edward R Knight¹, Nina H Leung, Yvonne H Lin, Andrew R Cowley, David J Watkin, Amber L Thompson, Graeme Hogarth, James D E T Wilton-Ely

Affiliation

¹ Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UK OX1 3TA.

PMID: 19417934
DOI: 10.1039/b821947h

Abstract

Homobimetallic complexes of nickel, palladium and platinum, [(L2M)2(S2CNC4H8NCS2)]2+, are formed on reaction of the piperazine bis(dithiocarbamate) linker, KS2CNC4H8NCS2K, with [MCl2L2] (M=Ni, L2=dppe, dppf; M=Pd, L2=dppf; M=Pt, L=PEt3, PMePh2, PPh3, L2=dppf). [{Pd(C,N-C6H4CH2NMe2)}2(S2CNC4H8NCS2)] can be obtained in the same way. On reaction of [MCl2L2] (M=Pd, Pt) with the zwitterion S2CNC4H8NH2, a symmetrisation process occurs to yield a mixture of the complexes [M(S2CNC4H8NH2)L2]2+ and [(L2M)2(S2CNC4H8NCS2)]2+. However, the monometallic complexes [L2Ni(S2CNC4H8NH2)]2+ (L2=dppe, dppf) and [(L2Ni)2(S2CNC4H8NCS2)]2+ can be prepared without ready symmetrisation. Starting from the previously reported [(dppm)Ru(S2CNC4H8NH2)]2+, the heterotrimetallic products [(dppm)Ru(S2CNC4H8NCS2)M(dppf)]2+ (M=Pd, Pt) can be prepared without symmetrisation occurring. The crystal structures of five complexes are reported. The metalla-dithiocarbamate complexes [L2Ni(S2CNC4H8NCS2)] (L2=dppe, dppf) were used to functionalise the surface of gold nanoparticles by the displacement of a citrate shell to yield NiAu and FeNiAu materials.