87350-38-7Relevant academic research and scientific papers
Transition Metal Complexes with Sulfur Ligands, V. Synthesis, Reactivity and Structure of Carbonyl-, Phosphine-, and Hydrazin-Iron(II) Complexes with Two and Fourdentate Sulfur Ligands
Sellmann, Dieter,Lanzrath, Guenther,Huttner, Gottfried,Zsolnai, Laszlo,Krueger, Carl,Claus, K. H.
, p. 961 - 981 (2007/10/02)
Reaction of FeCl2*4H2O with dttd(2-), the dianion of 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane, leads to the solvated , which coordinates CO, PMe3 and N2H4 yielding , , , and , respectively.With H2S and the Fe(III) complex (PPN)2 is obtained.PPh3 cannot be coordinated to , whereas the reaction between and LiSC6H4SCH3 yields besides the major product .A PPh3 complex can be obtained also with o-benzenedithiolate, C6H4S2(2-): Reacting with Li2S2C6H4 yields the binuclear 2.Oxidation of by various agents leads to 2 without evidence of formation of a N2 complex intermediate.Nucleophilic attack of by lithium organyls as e.g.LiPh leads to the benzoylato complex ; the structures of the starting complex as well as of the adduct have been elucidated by X-ray structure determination.Nucleophilic attack of the corresponding by LiPh occurs reversibly at the Fe center; by cleavage of a Fe-S bond (-) is formed, where dttd' is acting as a tridentate ligand.This result shows how the reactions of formally equivalent complexes like and depend strongly upon the denticity of the sulfur ligands.The dependance upon the character of the nucleophilic agent is shown by the reaction of with Li; in this case again a CO ligand is attacked reversibly yielding the formyl complex , the structureof which could be elucidated so far only spectroscopically as well as by elemental analysis. (-) forms salts like e.g. (AsPh4); in solution they slowly loose CO yielding e.g. binuclear (AsPh4)22.Attempts to isolate the anion as (+) salt lead to the loss of CO as well as of phenyl ligands yielding the paramagnetic , which is also obtained directly from and TMED.The phenyl complex 2(2-) is also formed by reaction of with LiPh; on reaction with dimethyl-formamide it yields 2.A series of the above described compounds has been investigated by Moessbauer spectroscopy. - Key words: Iron(II) Sulfur Complexes, Synthesis, Reactions, X-Ray
