Ohki, Yasuhiro published the artcileSynthesis, Structures, and Electronic Properties of [8Fe-7S] Cluster Complexes Modeling the Nitrogenase P-Cluster, Safety of 2,4,6-Triisopropylbenzenethiol, the publication is Journal of the American Chemical Society (2009), 131(36), 13168-13178, database is CAplus and MEDLINE.
High-yield synthesis of the Fe-S cluster [{N(SiMe3)2}{SC(NMe2)2}Fe4S3]2(¦Ì6-S) {¦Ì-N(SiMe3)2}2 (1), which reproduces the [8Fe-7S] core structure of the nitrogenase PN-cluster, was achieved via two pathways: (1) Fe{N(SiMe3)2}2 + HSTip (Tip = 2,4,6-iPr3C6H2) + tetramethylthiourea (SC(NMe2)2) + elemental S (S8); and (2) Fe3{N(SiMe3)2}2(¦Ì-STip)4 (2) + HSTip + SC(NMe2)2 + S8. The thiourea and terminal amide ligands of 1 are replaceable by thiolate ligands upon treatment with thiolate anions and thiols at -40¡ã, resp., and [8Fe-7S] clusters bearing two to four thiolate ligands were synthesized and their structures were determined by x-ray anal. The structures of these model [8Fe-7S] clusters all closely resemble that of the reduced form of P-cluster (PN) having 8Fe(II) centers, while their 6Fe(II)-2Fe(III) oxidation states correspond to the oxidized form of P-cluster (POX). The cyclic voltammograms of the [8Fe-7S] clusters reveal two quasi-reversible 1-electron reduction processes, leading to the 8Fe(II) state that is the same as the PN-cluster, and the synthetic models demonstrate the redox behavior between the two major oxidation states of the native P-cluster. Replacement of the SC(NMe2)2 ligands in 1 with thiolate anions led to more neg. reduction potentials, while a slight pos. shift occurred upon replacement of the terminal amide ligands with thiolates. The clusters 1, (NEt4)2[{N(SiMe3)2}(SC6H4-4-Me)Fe4S3]2(¦Ì6-S){¦Ì-N(SiMe3)2}2 (3a), and [(SBtp){SC(NMe2)2}Fe4S3]2(¦Ì6-S){¦Ì-N(SiMe3)2}2 (5; Btp = 2,6-(SiMe3)2C6H3) are EPR silent at 4-100 K, and their temperature-dependent magnetic moments indicate a singlet ground state with antiferromagnetic couplings among the Fe centers. The 57Fe Mossbauer spectra of these clusters are consistent with the 6Fe(II)-2Fe(III) oxidation state, each exhibiting two doublets with an intensity ratio of ?1:3, which are assignable to Fe(III) and Fe(II), resp. Comparison of the quadrupole splittings for 1, 3a, and 5 indicated that two Fe(III) sites of the clusters are the peripheral Fe atoms.
Journal of the American Chemical Society published new progress about 22693-41-0. 22693-41-0 belongs to catalysis-chemistry, auxiliary class Other Functionalization Reagent, name is 2,4,6-Triisopropylbenzenethiol, and the molecular formula is C15H24S, Safety of 2,4,6-Triisopropylbenzenethiol.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia