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

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

doi:10.1021/ic401936w

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

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

31 Citations (Scopus)

Abstract

The new DO3A-derived dithiocarbamate ligand, DO3A-^tBu-CS ₂K, 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=CHC₆H ₄Me-4)Cl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S₂C-DO3A-^tBu)(dppm) ₂]⁺ and [Ru(CH=CHC₆H₄Me-4)(S ₂C-DO3A-^tBu)(CO)(PPh₃)₂], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C ₆H₄CH₂NMe₂)Cl]₂ and [PtCl₂(PPh₃)₂] form the dithiocarbamate compounds, [Pd(C,N-C₆H₄CH₂NMe ₂)(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(PR ₃)] (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(S ₂C-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@S ₂C-DO3A-Gd with an r¹ value of 4.7 mM^-1 s ^-1 per chelate and 1500 mM^-1 s^-1 per object.

Original language	English
Pages (from-to)	1989-2005
Number of pages	17
Journal	INORGANIC CHEMISTRY
Volume	53
Issue number	4
DOIs	https://doi.org/10.1021/ic401936w
Publication status	Published - 17 Feb 2014

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@article{f57e46be2973425287865f26823c2575,

title = "Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-elements",

abstract = "The new DO3A-derived dithiocarbamate ligand, DO3A-tBu-CS 2K, 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=CHC6H 4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S2C-DO3A-tBu)(dppm) 2]+ and [Ru(CH=CHC6H4Me-4)(S 2C-DO3A-tBu)(CO)(PPh3)2], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C 6H4CH2NMe2)Cl]2 and [PtCl2(PPh3)2] form the dithiocarbamate compounds, [Pd(C,N-C6H4CH2NMe 2)(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(PR 3)] (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(S 2C-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@S 2C-DO3A-Gd with an r1 value of 4.7 mM-1 s -1 per chelate and 1500 mM-1 s-1 per object.",

author = "Simon Sung and Holly Holmes and Luke Wainwright and Anita Toscani and Stasiuk, {Graeme J.} and White, {Andrew J.P.} and Bell, {Jimmy D.} and Wilton-Ely, {James D.E.T.}",

year = "2014",

month = feb,

day = "17",

doi = "10.1021/ic401936w",

language = "English",

volume = "53",

pages = "1989--2005",

journal = "INORGANIC CHEMISTRY",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-elements

AU - Sung, Simon

AU - Holmes, Holly

AU - Wainwright, Luke

AU - Toscani, Anita

AU - Stasiuk, Graeme J.

AU - White, Andrew J.P.

AU - Bell, Jimmy D.

AU - Wilton-Ely, James D.E.T.

PY - 2014/2/17

Y1 - 2014/2/17

N2 - The new DO3A-derived dithiocarbamate ligand, DO3A-tBu-CS 2K, 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=CHC6H 4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S2C-DO3A-tBu)(dppm) 2]+ and [Ru(CH=CHC6H4Me-4)(S 2C-DO3A-tBu)(CO)(PPh3)2], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C 6H4CH2NMe2)Cl]2 and [PtCl2(PPh3)2] form the dithiocarbamate compounds, [Pd(C,N-C6H4CH2NMe 2)(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(PR 3)] (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(S 2C-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@S 2C-DO3A-Gd with an r1 value of 4.7 mM-1 s -1 per chelate and 1500 mM-1 s-1 per object.

AB - The new DO3A-derived dithiocarbamate ligand, DO3A-tBu-CS 2K, 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=CHC6H 4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S2C-DO3A-tBu)(dppm) 2]+ and [Ru(CH=CHC6H4Me-4)(S 2C-DO3A-tBu)(CO)(PPh3)2], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C 6H4CH2NMe2)Cl]2 and [PtCl2(PPh3)2] form the dithiocarbamate compounds, [Pd(C,N-C6H4CH2NMe 2)(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(PR 3)] (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(S 2C-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@S 2C-DO3A-Gd with an r1 value of 4.7 mM-1 s -1 per chelate and 1500 mM-1 s-1 per object.

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U2 - 10.1021/ic401936w

DO - 10.1021/ic401936w

M3 - Article

C2 - 24495254

AN - SCOPUS:84894365418

SN - 0020-1669

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EP - 2005

JO - INORGANIC CHEMISTRY

JF - INORGANIC CHEMISTRY

IS - 4

ER -

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

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