Reisner, Erwin’s team published research in Inorganic Chemistry in 46 | CAS: 22693-41-0

Inorganic Chemistry 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, Application In Synthesis of 22693-41-0.

Reisner, Erwin published the artcileInfluence of Steric Hindrance on the Core Geometry and Sulfoxidation Chemistry of Carboxylate-rich Diiron(II) Complexes, Application In Synthesis of 22693-41-0, the publication is Inorganic Chemistry (2007), 46(24), 10229-10240, database is CAplus and MEDLINE.

The asym. terphenyl-2′-carboxylate ligand 3,5-dimethyl-1,1′:3′,1”-terphenyl-2′-carboxylate, –O2CArPh,Xyl, was prepared in high yield. This ligand facilitates the assembly of the diiron(II) complexes [Fe2(μ-O2CArTol)2(O2CArPh,Xyl)2(THF)2] [2, –O2CArTol = 2,6-di-p-tolylbenzoate], [Fe2(μ-O2CArTol)2(O2CArPh,Xyl)2(pyridine)2] (5), [Fe2(μ-O2CArPh,Xyl)2(O2CArPh,Xyl)2(THF)2] (3), and [Fe2(μ-O2CArPh,Xyl)2(O2CArPh,Xyl)2(pyridine)2] (6), all of which have a windmill geometry. The Fe-Fe distance of 3.355[10] Å in 6 is âˆ? Å shorter than that in the analog [Fe2(μ-O2CArTol)2(O2CArTol)2(pyridine)2] (4) and similar to the âˆ?.3 Å metal-metal separation at the active site of the reduced diiron(II) form of the soluble methane monooxygenase hydroxylase enzyme (MMOHred). Ortho-substituted picolyl-based ligands, 2-picSMe, 2-picSEt, 2-picStBu, 2-picSPh, 2-picSPh(Me3) (Ph(Me3) = mesityl), and 2-picSPh(iPr3) (Ph(iPr3) = 2,4,6-triisopropylphenyl), were prepared and allowed to react with [Fe2(μ-O2CAr)2(O2CAr)2(THF)2] to produce [Fe2(μ-O2CAr)3(O2CAr)(picSR)] (7–13, Ar = ArTol or ArPh,Xyl) complexes in 45-87% yields. The substrates tethered to the pyridine N-donor ligands picSR, where R = Me, Et, tBu, or Ph, coordinate to one Fe atom of the diiron(II) center by the N and S atoms to form a five-membered chelate ring. The Fe-S distance becomes elongated with increasing steric hindrance imparted by the R group. The most sterically hindered ligands, 2-picSPh(Me3) and 2-picSPh(iPr3), bind to the metal only through the pyridine N atom. The reactions of several of these complexes with dioxygen were studied, and the oxygenated products were analyzed by 1H NMR spectroscopy and GC/MS measurements following decomposition on a Chelex resin. The amount of sulfoxidation product is correlated with the Fe···S distance. The ratio of oxidized to unoxidized thioether substrate varies from 3.5, obtained upon oxygenation of the weakly coordinated 2-picSPh ligand in 10, to 1.0, obtained for the bulky 2-picSPh(iPr3) ligand in 12, for which the Fe-S distance is >4 Å. External thioether substrates were not oxidized when present in oxygenated solutions of paddlewheel and windmill diiron(II) complexes containing 1-methylimidazole or pyridine ligands, resp.

Inorganic Chemistry 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, Application In Synthesis of 22693-41-0.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia