12096-77-4Relevant academic research and scientific papers
Synthesis of Mono-and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S2C2Ph2)}6]
Adams, Harry,Morris, Michael J.,Robertson, Craig C.,Tunnicliffe, Helen C. I.
, p. 665 - 676 (2019/01/30)
The dithiolene transfer reaction between the nickel bis(dithiolene) complex [Ni(S2C2Ph2)2] and iron carbonyls has been re-investigated, and the conditions for the production of the dinuclear product [Fe2(μ-S2C2Ph2)(CO)6] have been optimized. Interception of a purple intermediate, thought to be [Fe(CO)3(S2C2Ph2)], in the reaction of [Fe(CO)5] with [Ni(S2C2Ph2)2] by the addition of PPh3 affords the new dark blue mononuclear complex [Fe(CO)2(PPh3)(S2C2Ph2)] in good yield. The fate of the nickel dithiolene fragments in these reactions has also been established by crystallographic characterization of the hexamer [{Ni(S2C2Ph2)}6] and the trinuclear cluster [Ni3(μ-S2C2Ph2)3(PPh3)2]. The substitution reactions of [Fe2(μ-S2C2Ph2)(CO)6] with PPh3 in the presence of Me3NO to give monosubstituted [Fe2(μ-S2C2Ph2)(CO)5(PPh3)] and disubstituted [Fe2(μ-S2C2Ph2)(CO)4(PPh3)2] are also reported.
Unexpected fragmentation of phenyldithiobenzoate, formation and X-ray structure of [μ,η2(S,S)-1,2-(dithio)-1,2-(diphenylethylene)] diiron hexacarbonyl complex
Mousser, Hénia,Darchen, André,Mousser, Abdelhamid
, p. 786 - 791 (2010/06/16)
The reaction of Fe2(CO)9 with phenyldithiobenzoate PhCS2Ph 1 afforded four colored compounds: [(μ-η3(C,S,S)PhCS2Ph)]Fe2(CO) 6 2, (μ-S)2Fe3(CO)9 3, (μ-SPh)2Fe2(CO)6 4 and [μ-η2(S,S)][PhC(S){double bond, long}C(S)Ph]Fe2(CO)6 5. Complex 5 was characterized by X-ray crystallography. The formation of complexes 4 and 5 was unexpected since it involved a fragmentation of the organic ligand 1 during its reaction with Fe2(CO)9. The electrochemical studies of 1, complexes 2 and 3 were undertaken in order to get information about the chemical behaviors of the intermediates generated by electron transfer. The results of cyclic voltammetry studies of 2 and 1 suggested that the reaction of 1 with Fe2(CO)9 involved two competitive reactions: (i) a thermal reaction which led to the expected compounds 2 and 3 and (ii) an electron transfer reaction involving a fragmentation of starting ligand 1 led to the unexpected complex 5. The required electrons may be provided by iron during the thermal decay of complexes 2 or 3 or Fe2(CO)9.
