在羧酸盐桥连的二价铁（II）配合物中，与氮供体吡啶配体相连的硫化物、膦和苄基底物的氧化反应。

Oxidation of sulfide, phosphine, and benzyl substrates tethered to N-donor pyridine ligands in carboxylate-bridged diiron(II) complexes.

作者信息

Carson Emily C, Lippard Stephen J

机构信息

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02319, USA.

出版信息

J Am Chem Soc. 2004 Mar 24;126(11):3412-3. doi: 10.1021/ja031806c.

DOI:10.1021/ja031806c

PMID:15025454

Abstract

Substituted pyridines were employed to prepare a series of terphenylcarboxylate-bridged diiron(II) compounds to mimic aspects of the chemistry at the active sites of bacterial multicomponent monooxygenases, including soluble methane monooxygenase (sMMO) and toluene monooxygenase (ToMO). Complexes of general formula [Fe2(O2CArTol)4L], L = 2, 3, or 4-pyridyldiphenylphosphine, 2-pyridylphenylsulfide, or 2-benzylpyridine and ArTol = 2,6-di(p-tolyl)benzoate, were synthesized and characterized by X-ray crystallography. Upon exposure of these compounds to dioxygen, ligand oxidation ensued and, in one case, proceeded catalytically.

摘要

使用取代吡啶制备了一系列联苯羧酸酯桥联的二价铁（II）化合物，以模拟细菌多组分单加氧酶活性位点的化学性质，包括可溶性甲烷单加氧酶（sMMO）和甲苯单加氧酶（ToMO）。合成了通式为[Fe2(O2CArTol)4L]的配合物，其中L = 2、3或4 - 吡啶基二苯基膦、2 - 吡啶基苯基硫醚或2 - 苄基吡啶，ArTol = 2,6 - 二（对甲苯基）苯甲酸酯，并通过X射线晶体学进行了表征。将这些化合物暴露于氧气中后，配体发生氧化，在一种情况下，氧化反应具有催化性。