Effects of Thiolate Ligation in Monoiron Hydrogenase (Hmd): Stability of the {Fe(CO)2}2+ Core with NNS Ligands was written by Xie, Zhu-Lin;Pennington, Doran L.;Boucher, Dylan G.;Lo, James;Rose, Michael J.. And the article was included in Inorganic Chemistry in 2018.Reference of 827-24-7 This article mentions the following:
In this work, we report the effects of NNS-thiolate ligands and nuclearity (monomer, dimer) on the stability of iron complexes related to the active site of mono-iron hydrogenase (Hmd, or “hydrogen-forming methylene-tetrahydromethanopterin dehydrogenase”). A thermally stable iron(II) dicarbonyl motif is the core feature of the active site, but the coordination features that lead to this property have not been independently evaluated for their contributions to the {Fe(CO)2}2+ stability. As such, non-bulky and bulky benzothiazoline ligands (thiolate precursors) have been synthesized and their iron(II) complexes characterized. The use of non-bulky thiolate ligands and low temperature crystallization result in isolation of the dimeric species [(NNS)2Fe2(CO)2(I)2] (1), [(NPhNS)2Fe2(CO)2(I)2] (2), and [(MeNNS)2Fe2(CO)2(I)2] (3), which exhibit dimerization via thiolato (μ2-S)2 bridges. In one particular case (unsubstituted NNS ligand), the pathway of decarbonylation and oxidation from 1 has been crystallog. elucidated, via isolation of the half-bis-ligated monocarbonyl dimer [(NNS)3Fe2(CO)]I (4) and the fully decarbonylated and oxidized mononuclear [(NNS)2Fe]I (5). The transformations of dicarbonyl complexes (1, 2 and 3) to monocarbonyl complexes (4, 6 and 7) has been monitored by UV/vis, demonstrating that 1 and 3 exhibit longer t1/2 (80 min and 75 min, resp.) than that of 2 (30 min), which can be related to the distortion of the ligand backbone. DFT calculations of isolated complexes and putative intermediates were used to corroborate the exptl. observed UV/vis and IR spectra. Finally, dimerization was prevented using a bulky ligand featuring a 2,6-dimethylphenyl substituent, which affords mononuclear iron dicarbonyl complex, [(NPhNSDMPh)Fe(CO)2Br] (8), identified by IR and NMR spectroscopies. The dicarbonyl complex decomposes to the decarbonylated [(NPhNSDMPh)2Fe] (9) within minutes at room temperature Overall, the work herein demonstrates that the thiolate moiety does not improve thermal stability to the {Fe(CO)2}2+ unit formed in the active site. In the experiment, the researchers used many compounds, for example, 2-Bromo-4-methyl-6-nitroaniline (cas: 827-24-7Reference of 827-24-7).
2-Bromo-4-methyl-6-nitroaniline (cas: 827-24-7) belongs to organobromine compounds. Organo bromine compounds are versatile compounds and are widely used in diverse fields. Organo bromine derivatives are used in the dye sector, as an indicator in analytical chemistry (Bromothymol blue is a popular indicator). The principal reactions for organobromides include dehydrobromination, Grignard reactions, reductive coupling, and nucleophilic substitution.Reference of 827-24-7
Referemce:
Bromide – Wikipedia,
bromide – Wiktionary