Multimetallic assemblies using piperazine-based dithiocarbamate building blocks.

Multimetallic assemblies using piperazine-based dithiocarbamate building blocks. Research Abstract Details 

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Multimetallic assemblies using piperazine-based dithiocarbamate building blocks. Abstract Text:

Treatment of cis-[RuCl 2(dppm) 2] (dppm = bis(diphenylphosphino)methane) with dithiocarbamates, NaS 2CNR 2 (R = Me, Et) and [H 2NC 5H 10][S 2CNC 5H 10], yields cations [Ru(S 2CNR 2) 2(dppm) 2] (+) and [Ru(S 2CNC 5H 10) 2(dppm) 2] (+), respectively. The zwitterions S 2CNC 4H 8NHR (R = Me, Et) react with the same metal complex in the presence of base to yield [Ru(S 2CNC 4H 8NR)(dppm) 2] (+). Piperazine or 2,6-dimethylpiperazine reacts with carbon disulfide to give the zwitterionic dithiocarbamate salts H 2NC 4H 6(R 2-3,5)NCS 2 (R = H; R = Me), which form the complexes [Ru(S 2CNC 4H 6(R 2-3,5)NH 2)(dppm) 2] (2+) on reaction with cis-[RuCl 2(dppm) 2]. Sequential treatment of [Ru(S 2CNC 4H 8NH 2)(dppm) 2] (2+) with triethylamine and carbon disulfide forms the versatile metalla-dithiocarbamate complex [Ru(S 2CNC 4H 8NCS 2)(dppm) 2] which reacts readily with cis-[RuCl 2(dppm) 2] to yield [{Ru(dppm) 2} 2(S 2CNC 4H 8NCS 2)]. Reaction of [Ru(S 2CNC 4H 8NCS 2)(dppm) 2] with [Os(CH=CHC 6H 4Me-4)Cl(CO)(BTD)(PPh 3) 2] (BTD = 2,1,3-benzothiadiazole), [Pd(C 6H 4CH 2NMe 2)Cl] 2, [PtCl 2(PEt 3) 2], and [NiCl 2(dppp)] (dppp = 1,3-bis(diphenylphosphino)propane) results in the heterobimetallic complexes [(dppm) 2Ru(S 2CNC 4H 8NCS 2)ML n )] ( m+ ) (ML n = Os(CH=CHC 6H 4Me-4)(CO)(PPh 3) 2] (+), m = 1; ML n = Pd( C,N-C 6H 4CH 2NMe 2), m = 1; ML n = Pt(PEt 3) 2, m = 2; ML n = Ni(dppp), m = 2). Reaction of [NiCl 2(dppp)] with H 2NC 4H 8NCS 2 yields the structurally characterized compound, [Ni(S 2CNC 4H 8NH 2)(dppp)] (2+), which reacts with base, CS 2, and cis-[RuCl 2(dppm) 2] to provide an alternative route to [(dppm) 2Ru(S 2CNC 4H 8NCS 2)Ni(dppp)] (+). A further metalla-dithiocarbamate based on cobalt, [CpCo(S 2CNC 4H 8NH 2)(PPh 3)] (2+), is formed by treatment of CpCoI 2(CO) with S 2CNC 4H 8NH 2 followed by PPh 3. Further reaction with NEt 3, CS 2, and cis-[RuCl 2(dppm) 2] yields [(Ph 3P)CpCo(S 2CNC 4H 8NCS 2)Ru(dppm) 2] (2+). Heterotrimetallic species of the form [{(dppm) 2Ru(S 2CNC 4H 8NCS 2)} 2M] (2+) result from the reaction of [Ru(S 2CNC 4H 8NCS 2)(dppm) 2] and M(OAc) 2 (where M = Ni, Cu, Zn). Reaction of [Ru(S 2CNC 4H 8NCS 2)(dppm) 2] with Co(acac) 3 and LaCl 3 results in the formation of the compounds [{(dppm) 2Ru(S 2CNC 4H 8NCS 2)} 3Co] (3+) and [{(dppm) 2Ru(S 2CNC 4H 8NCS 2)} 3La] (3+), respectively. The electrochemical behavior of selected examples is also reported.

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Multimetallic assemblies using piperazine-based dithiocarbamate building blocks. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Inorganic chemistry

VOLUME: 47

Page Numbers: 9642-53

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ISSN: 1520-510X

DAY: 24

MONTH: 09

YEAR: 2008

Multimetallic assemblies using piperazine-based dithiocarbamate building blocks. Information

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LANGUAGE: eng

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AFFILIATION: Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, U.K., Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K. james.wilton-ely@chem.ox.ac.uk, g.hogarth@ucl.ac.uk.

Country: United States

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MEDLINETA: Inorg Chem

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