title: Bifunctional Chalcogen Linkers for the Stepwise Generation of Multimetallic Assemblies and Functionalized Nanoparticles.
abstract: The disulfide ligand (SC6H4CO2H-4)2acts as a simple but versatile linker for a range of group 8 transition metals through reaction of the oxygen donors. This leads to a range of homobimetallic ruthenium and osmium alkenyl compounds, [{M(CH═CHR)(CO)(PPh3)2(O2CC6H4S-4)}2] (M = Ru, Os; R = C6H4Me-4). Additional metal-based functionality can be added through the use of precursors incorporating rhenium bipyridine units (R = (bpy)ReCl(CO)3). The more robust diphosphine ligands in [{Ru(dppm)2(O2CC6H4S-4)}2]2+(dppm = diphenylphosphinomethane) allow reduction of the disulfide bond with sodium borohydride to yield the thiol complex [Ru(O2CC6H4SH-4)(dppm)2]+. This complex reacts with [AuCl(PPh3)] to afford the bimetallic compound [Ru(dppm)2(O2CC6H4S-4)Au(PPh3)]+. However, an improved route to the same and related heterobimetallic compounds is provided by the reaction of cis-[RuCl2(dppm)2] with [Au(SC6H4CO2H-4)(L)] (L = PPh3, PCy3, PMe3, IDip) in the presence of base and NH4PF6(IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The heterotrimetallic compound [Au(SC6H4CO2Ru(dppm)2)2]+is accessible through the reaction of the homoleptic gold(I) dithiolate [Au(SC6H4CO2H-4)2]PPN (PPN = bis(triphenylphosphine)iminium) with cis-[RuCl2(dppm)2]. Without departure from the same methodology, greater complexity can be incorporated into the system to provide the penta- and heptametallic assemblies [(dppf){AuSC6H4CO2Ru(dppm)2}2]2+and [(dppf){AuSC6H4CO2Os(CH═CH-bpyReCl(CO)3)(CO)(PPh3)2}2]. The same stepwise approach provides the dinuclear organometallic complexes [(L)Au(SC6H4CO2-4)M(CH═CHC6H4Me-4)(CO)(PPh3)2] (M = Ru, Os; L = PPh3, IDip). Complexes containing three metals from different groups of the periodic table [(L)Au(SC6H4CO2-4)M{CH═CH-bpyReCl(CO)3}(CO)(PPh3)2] (M = Ru, Os) can also be prepared, with one ruthenium example (L = PPh3) being structurally characterized. In order to illustrate the versatility of this approach, the synthesis and characterization (IR and NMR spectroscopy, TEM, EDS, and TGA) of the functionalized gold and palladium nanoparticles Au@[SC6H4CO2Ru(dppm)2]+and Pd@[SC6H4CO2Ru(dppm)2]+is reported.
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Jonathan A
authors.initials: JA
authors.lastname: Robson
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.|Departament de Química Inorgànica, Universitat de Barcelona , Martí Franquès 1-11, 08028 Barcelona, Spain.
authors.forename: Ferran
authors.initials: F
authors.lastname: Gonzàlez de Rivera
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Khairil A
authors.initials: KA
authors.lastname: Jantan
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Margot N
authors.initials: MN
authors.lastname: Wenzel
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.affiliation: Departament de Química Inorgànica, Universitat de Barcelona , Martí Franquès 1-11, 08028 Barcelona, Spain.
authors.forename: Oriol
authors.initials: O
authors.lastname: Rossell
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: James D E T
authors.identifier: http://orcid.org/0000-0002-5192-3038
authors.initials: JD
authors.lastname: Wilton-Ely