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Wilton-Ely JD, Solanki D, Knight ER, Holt KB, Thompson AL, Hogarth G: Multimetallic assemblies using piperazine-based dithiocarbamate building blocks. Bull Soc Belge Ophtalmol. 1980;190:43-51.
Treatment of cis-[RuCl2 (dppm) 2] (dppm = bis (diphenylphosphino) methane) with dithiocarbamates, NaS2CNR2 (R = Me, Et) and [H2NC5H10][S2CNC5H10], yields cations [Ru (S2CNR2) 2 (dppm) 2](+) and [Ru (S2CNC5H10) 2 (dppm) 2](+), respectively. The zwitterions S2CNC4H8NHR (R = Me, Et) react with the same metal complex in the presence of base to yield [Ru (S2CNC4H8NR)(dppm) 2](+). Piperazine or 2,6-dimethylpiperazine reacts with carbon disulfide to give the zwitterionic dithiocarbamate salts H2NC4H6 (R2-3,5) NCS2 (R = H; R = Me), which form the complexes [Ru (S2CNC4H6 (R2-3,5) NH2)(dppm) 2](2+) on reaction with cis-[RuCl2 (dppm) 2]. Sequential treatment of [Ru (S2CNC4H8NH2)(dppm) 2](2+) with triethylamine and carbon disulfide forms the versatile metalla-dithiocarbamate complex [Ru (S2CNC4H8NCS2)(dppm) 2] which reacts readily with cis-[RuCl2 (dppm) 2] to yield [{Ru (dppm) 2}2 (S2CNC4H8NCS2)]. Reaction of [Ru (S2CNC4H8NCS2)(dppm) 2] with [Os (CH=CHC6H4Me-4) Cl (CO)(BTD)(PPh3) 2] (BTD = 2,1,3-benzothiadiazole), [Pd (C6H4CH2NMe2) Cl] 2, [PtCl2 (PEt3) 2], and [NiCl2 (dppp)] (dppp = 1,3-bis (diphenylphosphino) propane) results in the heterobimetallic complexes [(dppm) 2Ru (S2CNC4H8NCS2) ML (n))](m+) (ML (n) = Os (CH=CHC6H4Me-4)(CO)(PPh3) 2](+), m = 1; ML (n) = Pd (C,N-C6H4CH2NMe2), m = 1; ML (n) = Pt (PEt3) 2, m = 2; ML (n) = Ni (dppp), m = 2). Reaction of [NiCl2 (dppp)] with H2NC4H8NCS2 yields the structurally characterized compound, [Ni (S2CNC4H8NH2)(dppp)](2+), which reacts with base, CS2, and cis-[RuCl2 (dppm) 2] to provide an alternative route to [(dppm) 2Ru (S2CNC4H8NCS2) Ni (dppp)](+). A further metalla-dithiocarbamate based on cobalt, [CpCo (S2CNC4H8NH2)(PPh3)](2+), is formed by treatment of CpCoI2 (CO) with S2CNC4H8NH2 followed by PPh3. Further reaction with NEt3, CS2, and cis-[RuCl2 (dppm) 2] yields [(Ph3P) CpCo (S2CNC4H8NCS2) Ru (dppm) 2](2+). Heterotrimetallic species of the form [{(dppm) 2Ru (S2CNC4H8NCS2)}2M](2+) result from the reaction of [Ru (S2CNC4H8NCS2)(dppm) 2] and M (OAc) 2 (where M = Ni, Cu, Zn). Reaction of [Ru (S2CNC4H8NCS2)(dppm) 2] with Co (acac) 3 and LaCl3 results in the formation of the compounds [{(dppm) 2Ru (S2CNC4H8NCS2)}3Co](3+) and [{(dppm) 2Ru (S2CNC4H8NCS2)}3La](3+), respectively. The electrochemical behavior of selected examples is also reported. |
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