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Bifunctional chalcogen linkers for the stepwise generation of multimetallic assemblies and functionalized nanoparticles

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Wilton-Ely DOI 10.1021acs.inorgchem.6b02409 AAM.pdfAccepted version2.51 MBAdobe PDFView/Open
Title: Bifunctional chalcogen linkers for the stepwise generation of multimetallic assemblies and functionalized nanoparticles
Authors: Robson, JA
Gonzàlez de Rivera, F
Jantan, KA
Wenzel, MN
White, AJ
Rossell, O
Wilton-Ely, JD
Item Type: Journal Article
Abstract: The disulfide ligand (SC6H4CO2H-4)2 acts 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.
Issue Date: 5-Dec-2016
Date of Acceptance: 1-Dec-2016
URI: http://hdl.handle.net/10044/1/43334
DOI: http://dx.doi.org/10.1021/acs.inorgchem.6b02409
ISSN: 1520-510X
Publisher: American Chemical Society
Start Page: 12982
End Page: 12996
Journal / Book Title: Inorganic Chemistry
Volume: 55
Issue: 24
Copyright Statement: © 2016 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://dx.doi.org/10.1021/acs.inorgchem.6b02409
Sponsor/Funder: Imperial College/Wellcome Trust Facility Network of Excellence scheme
Funder's Grant Number: P52862
Keywords: Inorganic & Nuclear Chemistry
0302 Inorganic Chemistry
0904 Chemical Engineering
0399 Other Chemical Sciences
Publication Status: Published
Conference Place: United States
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Faculty of Natural Sciences