Transition-metal dithiolene complexes. Part XII. Rhodium and iridium complexes
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 1621-1627
- https://doi.org/10.1039/j19700001621
Abstract
Both [Rh{S2C2(CN)2}n n–(n 1) and [Rh{S2C2(CN)2}3]2– have been isolated from the reaction of Rh2(OAc)4 and NaS(CN)C:C(CN)SNa. the cis-dicarbonyls [Rh(CO)2S2C2(CN)2]–, [Rh(CO)2S2C:C(CN)]– 2 and [Rh(CO)2(S2C6H3Me)]– were prepared by treatment of Rh2(CO)4Cl2 with the appropriate dithiolate dianion, and evidence for the existence of [Rh(CO)2(S2C6Cl4)]– is presented. [Rh(CO)2S2C2(CN)2]– undergoes substitution reactions with triphenylphosphine, triethyl phosphite, and bis(trifluoromethyl)dithieten, S2C2(CF3)′, giving [Rh(CO)(PPh3)S2C2(CN)2]–, [Rh{P(OPh)3}2S2C2(CN)2]–, and [RhS4C4(CN)(CF3)2]n n–(n 1), respectively. The reactions of [Rh(CO)(PPh3)S2C2(CN)2]– with iodine, mercury(II) chloride, mercury(II) cyanide, tetracyanoethylene, and sulphur dioxide are briefly described. Treatment of M(CO)(PPh3)2Cl (M = Rh or Ir) with S2C2(CF3)2 affords M2(PPh3)2{S2C2(CF3)2}3 in addition to some apparently trinuclear species. Reaction of Rh2(CO)4Cl2 with S2C2(CF3)2 appears to give [Rh(CO)S2C2(CF3)2]3 –. Many of the compounds have been examined voltammetrically, and some undergo electron transfer reactions.Keywords
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