142457-46-3Relevant academic research and scientific papers
Transition Metal Complexes with Sulfur Ligands, XC. Synthesis, Acid Base and Redox Reactions of : A Search for Model Complexes for the Nickel Sites in Hydrogenases and CO-Dehydrogenases. ('N2H2S2'2- = 1,2-Ethanediamine-N,N'-bis(2-benzenethiolate)(2-)>
Sellmann, Dieter,Prechtel, Werner,Knoch, Falk,Moll, Matthias
, p. 1411 - 1423 (2007/10/02)
, 1 forms from Ni(II) salts and the tetradentate thiolate-amine ligand 'N2H2S2'2- (2), or by reduction of the Schiff base complex (gma2- = glyoxal-bis(2-mercaptoanilide(2-))> with NaBH4.Bases easily deprotonate 1 to yield the 2- dianion, which is extremely easily oxidized to give the Ni(II) monoanion - which was isolated as , 4, and characterized by X-ray structure analysis. 4 contains a distorted square planar NiN2S2 core, in which two thiolate-S and two amido-N donors are surrounding the nickel atom.Deprotonatonation of 1 was further substantiated by H+/D+ exchange to give and by alkylation.Consecutive reaction of 1 with n-BuLi and CH3I leads to fourfold methylation of 1 yielding , 8, while alkylation of 1 by CH3I in the absence of bases yields , 5, in which the thiolate donors have been alkylated.X-ray structure analysis shows 8 to contain a distorted octahedral NiN2S2I2 core with two sulfur atoms occupying axial trans positions and two nitrogen and two iodine atoms occupying equatorial cis positions. 1 also forms by reaction of with 'N2H2S2'-H2, which is explained by a series of oxidative addition and reductive elimination reactions.Palladium and platinium homologues , 9 and , 10, were synthesized from (M = Pd, Pt) and 'N2H2S2'-H2, and exhibit analogues reactivity as 1. Key Words: Nickel Thiolate-Amine Complexes, reactions, Thioether-amine Ligands, Palladium and Platinium Derivatives, X-Ray
