Multimetallic Complexes and Functionalized Gold Nanoparticles Based on a Combination of d- and f-Elements

详细信息    查看全文

• 作者：Simon Sung ; Holly Holmes ; Luke Wainwright ; Anita Toscani ; Graeme J. Stasiuk ; Andrew J. P. White ; Jimmy D. Bell ; James D. E. T. Wilton-Ely
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 17, 2014
• 年：2014
• 卷：53
• 期：4
• 页码：1989-2005
• 全文大小：693K
• ISSN：1520-510X

文摘

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鈺怌HC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S₂C-DO3A-^tBu)(dppm)₂]⁺ and [Ru(CH鈺怌HC₆H₄Me-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路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^鈥? s^鈥? 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^鈥? s^鈥? per chelate and 1500 mM^鈥? s^鈥? per object.