109334-45-4Relevant academic research and scientific papers
Transition Metal Complexes with Sulfur Ligands, CVIII. A Facile Synthesis of the Tertiary Amine-thiolato Ligand 'S2N2Me2'(2-). Influence of the Anminomethylation on the Coordination Chemistry of Nickel and Ruthenium Complexes with Frameworks ( R = H, CH3)....
Sellmann, Dieter,Ruf, Richard,Knoch, Falk,Moll, Matthias
, p. 791 - 801 (2007/10/02)
In a single pot synthesis consecutive reaction of the tetradentate amine-thiole H2-'S2N2H2' 2 ('S2N2H2'(2-) = 1,2-ethanediamino-N,N'-bis(2-benzenethiolato)(2-)), with and benzyl chloride (BzCl) yields the amine-thioether 'Bz2S2N2H2' which gives the tertiary amine-thioether 'Bz2S2N2Me2' when reacted with further and CH3I.Removal of the benzyl groups with an excess of sodium and acidification with hydrochloric acid finally yield H2-'S2N2Me2' 1 ('S2N2Me2'(2-) = 1,2-ethanediamino-N,N'-dimethyl-N,N'-bis(2-benzenethiolato)(2-). 1 and 2 have been characterized by X-ray structure analysis.With *4H2O, 1 yields racemic 3 in a diastereospecific reaction.Crystallization of 3 leads to spontaneous resolution of the racemate.By X-ray structure analysis of 3 the absolute configuration in the single crystal examined was determined using Roger's μ-refinement (μ = 1.00(4)).Upon reaction with , LiOMe and CO, 1 yields 5.Spectroscopic data indicate that 5 and the parent complex differ with respect to their core structures.Influence of the amine methylation on structure and reactivity of complexes with cores, R = H, Me, is discussed. - Keywords: Aminomethylation, Nickel and Ruthenium Sulfur Complexes, Synthesis, X-Ray
Molybdenum(VI) and Molybdenum(V) Complexes with N,N'-Dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine. Electrochemical and Electron Paramagnetic Resonance Models for the Molybdenum(VI/V) Centers of the Molybdenum Hydroxylases and Related Enzymes
Dowerah, Dulal,Spence, Jack T.,Singh, Raghuvir,Wedd, Anthony G.,Wilson, Graham L.,et al.
, p. 5655 - 5665 (2007/10/02)
As models for the molybdenum(VI/V) centers of the molybdenum hydroxylases and related enzymes, MoO2L and MoOClL (LH2=N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine) have been synthesized.The structure of MoO2L hasbeen determined by X-ray crystallography.The compound crystallizes in space group P21/n, with a=10.049(2) Angstroem, b=14.538(2) Angstroem, c=12.143(1) Angstroem, β=103.73(1) deg, and Z=4.MoO2L is six-coordinate with approximate C2 symmetry, with the two thiolate S atoms trans to one another and the two tertiary amine N atoms approximately trans to the terminal oxo groups.MoO2L undergoes reversible one-electron reduction on both cyclic voltammetric and coulometric time scales to give various oxo-Mo(V) complexes.The EPR spectra of these complexes including 98Mo, 2H, and 17O substituted species, are consistent with formulation as -, cis-MoO(OH)L, -, and cis-MoO(SH)L. 1H coupling constants for cis-MoO(OH)L (1.65 mT) and cis-MoO(SH)L (1.05 mT) and the 17O coupling constants for Mo17O(17OH)L (0.25 and 0.82 mT), - (0.43 mT), and Mo17O(SH)L (0.22 mT) have been measured.MoOClL exhibit reversible one-electron electrochemical reduction in its cyclic voltammogram but decomposes upon coulometric reduction.EPR data indicate it is trans-MoOClL.Substitution of Cl- by OH-, F-, and SH- has been effected in solution.The implications of the results for the structures of Mo(VI/V) centers of the enzymes are discussed.In particular, MoVOS(OR) and MoVO(SH)(OR) (OR=bound product) are suggested as the centers responsible for the "very rapid" and "rapid" EPR signals of xanthine oxidase.An MoVO(OH) center appears to be involved in the "slow" EPR signal of xanthine oxidase and the low pH forms of sulfite axidase and nitrate reductase; the high pH forms of the latter enzymes, however, do not apear to involve a conjugate base MoVO2 center.
