153511-19-4Relevant academic research and scientific papers
Conformational Effects of [Ni2(μ-ArS)2] Cores on Their Electrocatalytic Activity
Mondragón-Díaz, Alexander,Robles-Marín, Elvis,Murueta-Cruz, Brenda A.,Aquite, Juan C.,Martínez-Alanis, Paulina R.,Flores-Alamo, Marcos,Aullón, Gabriel,Benítez, Luis Norberto,Castillo, Ivan
, p. 3301 - 3312 (2019/09/13)
Two nickel complexes supported by tridentate NS2 ligands, [Ni2(κ-N,S,S,S′-NPh{CH2(MeC6H2R′)S}2)2] (1; R′=3,5-(CF3)2C6H3) and [Ni2(κ-N,S,S,S′-NiBu{CH2C6H4S}2)2] (2), were prepared as bioinspired models of the active site of [NiFe] hydrogenases. The solid-state structure of 1 reveals that the [Ni2(μ-ArS)2] core is bent, with the planes of the nickel centers at a hinge angle of 81.3(5)°, whereas 2 shows a coplanar arrangement between both nickel(II) ions in the dimeric structure. Complex 1 electrocatalyzes proton reduction from CF3COOH at ?1.93 (overpotential of 1.04 V, with icat/ip≈21.8) and ?1.47 V (overpotential of 580 mV, with icat/ip≈5.9) versus the ferrocene/ferrocenium redox couple. The electrochemical behavior of 1 relative to that of 2 may be related to the bent [Ni2(μ-ArS)2] core, which allows proximity of the two Ni???Ni centers at 2.730(8) ?; thus possibly favoring H+ reduction. In contrast, the planar [Ni2(μ-ArS)2] core of 2 results in a Ni???Ni distance of 3.364(4) ? and is unstable in the presence of acid.
Effective synthesis of ortho-substituted trithiophenol amines by Miyazaki-Newman-Kwart rearrangement
Gjoka, Blerina,Romano, Francesco,Zonta, Cristiano,Licini, Giulia
experimental part, p. 5636 - 5640 (2011/11/29)
An efficient synthesis of ortho-substituted trithiophenol amines from commercially available salicaldehydes by Miyazaki-Newman-Kwart rearrangement/threefold reductive amination is reported. The rearrangement has been carried out on salicaldehyde-O-thiocarbamates using microwave induced heating, which furnishes a series of thiosalicaldehyde-S-carbamates in high yield. The thiocarbamate has three roles: it enables effective S-O rearrangement, acts as a protecting group during the threefold reductive amination and can be easily removed under reductive conditions. The three-step synthesis has an overall yield ranging from 30-35 %, and it enables access to a series of increasingly important C3v symmetric ligands in a structurally systematic way.
BICYCLOSULFONYL ACID (BCSA) COMPOUNDS AND THEIR USE AS THERAPEUTIC AGENTS
-
Page/Page column 80-81; 163, (2009/01/20)
This invention pertains generally to the field of therapeutic compounds, and more particularly, to certain bicyclosulfonyl acid (BCSA) compounds which act as inhibitors of Tumour Necrosis Factor-α Converting Enzyme (TACE). The compounds are useful in the
Conversion of some substituted phenols to the corresponding masked thiophenols, synthesis of a dinickel(n) dithiolate macrocyclic complex and isolation of some metal- And ligand-based oxidation products
Brooker, Sally,Caygill, Graham B.,Croucher, Paul D.,Davidson, Tony C.,Clive, Derrick L. J.,Magnuson, Stephen R.,Cramer, Stephen P.,Ralston, Corie Y.
, p. 3113 - 3121 (2007/10/03)
A modified preparation of the masked thiolate head unit 5-(2, 6-diformyl-4-methyIphenyl) dimethylthiocarbamate 6 is detailed and two new masked thiolate head units, 5-(2, 6-diformyl-4-tert-butylphenyl) dimethylthiocarbamate 7 and S-(2-formylphenyl) dimethylthiocarbamate 8, are prepared by this method. The synthesis, crystal structure, NMR spectra and electrochemical properties of the first macrocyclic complex to be derived from 7, [Ni2Ll](GO4)2, are discussed. Oxidation of [Ni2L2](CF3SO3)2 (L22- is derived from 6 and 1, 3-diaminopropane) with cerium(iv) ammonium nitrate led to the precipitation of the black complex [Ni2L2][Ce(NO3)6], which is believed to contain a single nickel(in) centre. This complex decomposes in DMF over time (24 hours) to form the red dinickel(n) complex [Ni2L2](NO3)2-2DMF which has been structurally characterised. Oxidation of [Ni2L3](CF3SO3)2 (L32- is derived from 6 and 1, 4-diaminobutane) with I2 results in ligand oxidation forming the metal free macrocycle (L3')2t which contains two five membered isothiazole rines. This is confirmed by the X-ray crystal structure determinations of (L3')(I, ), and (L3')(I):(I2)5. The Royal Society of Chemistry 2000.
