Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-Elements

Stasiuk, Graeme J.; Bell, Jimmy D.; Holmes, Holly; Sung, Simon; Toscani, Anita; Wainwright, Luke; White, Andrew J. P.; Wilton-Ely, James D. E. T.

Abstract

The new DO3A-derived dithiocarbamate ligand, DO3A-ᵗBu-CS₂K, is formed by treatment of the ammonium salt [DO3A-ᵗBu]HBr with K₂CO₃ and carbon disulfide. DO3A-ᵗBu-CS₂K reacts with the ruthenium complexes cis-[RuCl₂(dppm)₂] and [Ru(CH═CHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S₂C-DO3A-ᵗBu)(dppm)₂]+ and [Ru(CH═CHC₆H₄Me-4)(S₂C-DO3A-ᵗBu)(CO)(PPh₃)₂], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C6H4CH₂NMe₂)Cl]₂ and [PtCl2(PPh₃)₂] form the dithiocarbamate compounds, [Pd(C,N-C₆H₄CH₂NMe₂)(S₂C-DO3A-ᵗBu)] and [Pt(S₂C-DO3A-ᵗBu)(PPh₃)₂]+, under the same conditions. The linear gold complexes [Au(S₂C-DO3A-ᵗBu)(PR₃)] are formed by reaction of [AuCl(PR₃)] (R = Ph, Cy) with DO3A-ᵗBu-CS₂K. However, on reaction with [AuCl(tht)] (tht = tetrahydrothiophene), the homoleptic digold complex [Au(S2C-DO3A-ᵗBu)]₂ is formed. Further homoleptic examples, [M(S₂C-DO3A-ᵗBu)₂] (M = Ni, Cu) and [Co(S₂C-DO3A-ᵗBu)₃], are formed from treatment of NiCl₂·6H₂O, Cu(OAc)₂, or Co(OAc)₂, respectively, with DO3A-ᵗBu-CS₂K. The molecular structure of [Ni(S₂C-DO3A-ᵗBu)₂] was determined crystallographically. The tert-butyl ester protecting groups of [M(S₂C-DO3A-ᵗBu)₂] (M = Ni, Cu) and [Co(S₂C-DO3A-ᵗBu)₃] are cleaved by trifluoroacetic acid to afford the carboxylic acid products, [M(S₂C-DO3A)₂] (M = Ni, Cu) and [Co(S₂C-DO3A)₃]. Complexation with Gd(III) salts yields trimetallic [M(S₂C-DO3A-Gd)₂] (M = Ni, Cu) and tetrametallic [Co(S₂C-DO3A-Gd)₃], with r¹ values of 11.5 (Co) and 11.0 (Cu) mM⁻¹ s⁻¹ per Gd center. DO3A-ᵗBu-CS₂K can also be used to prepare gold nanoparticles, Au@S₂C-DO3A-ᵗBu, by displacement of the surface units from citrate-stabilized nanoparticles. This material can be transformed into the carboxylic acid derivative Au@S2C-DO3A by treatment with trifluoroacetic acid. Complexation with Gd(OTf)3 or GdCl3 affords Au@S₂C-DO3A-Gd with an r¹ value of 4.7 mM⁻¹ s⁻¹ per chelate and 1500 mM⁻¹ s⁻¹ per object.

Citation

Stasiuk, G. J., Bell, J. D., Holmes, H., Sung, S., Toscani, A., Wainwright, L., White, A. J. P., & Wilton-Ely, J. D. E. T. (2014). Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-Elements. Inorganic chemistry, 53(4), 1989-2005. https://doi.org/10.1021/ic401936w

• Acceptance Date: Jul 26, 2013
• Online Publication Date: Feb 4, 2014
• Publication Date: Feb 17, 2014
• Deposit Date: Feb 19, 2016
• Publicly Available Date: Feb 19, 2016
• Journal: Inorganic chemistry
• Print ISSN: 0020-1669
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 53
• Issue: 4
• Pages: 1989-2005
• DOI: https://doi.org/10.1021/ic401936w
• Keywords: Multimetallic; Dithiocarbamates; Nanoparticles; Images
• Public URL: https://hull-repository.worktribe.com/output/411122
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/ic401936w
• Additional Information: “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 http://pubs.acs.org/doi/abs/10.1021/ic401936w.”
• Contract Date: Feb 19, 2016