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.
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.
Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UK OX1 3TA.
Edward R
ER
Knight
Nina H
NH
Leung
Yvonne H
YH
Lin
Andrew R
AR
Cowley
David J
DJ
Watkin
Amber L
AL
Thompson
Graeme
G
Hogarth
James D E T
JD
Wilton-Ely