由羧酸盐桥连的非血红素二铁配合物进行的催化氧化反应。

Catalytic oxidation by a carboxylate-bridged non-heme diiron complex.

作者信息

Tshuva Edit Y, Lee Dongwhan, Bu Weiming, Lippard Stephen J

机构信息

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.

出版信息

J Am Chem Soc. 2002 Mar 20;124(11):2416-7. doi: 10.1021/ja017890i.

DOI:10.1021/ja017890i

PMID:11890772

Abstract

The synthesis of a sterically hindered di(mu-carboxylato)diiron(II) complex bearing terminal N,N',N"-trimethyl-1,4,7-triazacyclononane (Me(3)TACN) ligands and its reaction with dioxygen to afford a (mu-oxo)di(mu-carboxylato)diiron(III) complex are described. Both compounds initiate catalytic oxo transfer with O(2) as the terminal oxidant, converting phosphines to phosphine oxides, dimethyl sulfide to dimethyl sulfoxide, and dibenzylamine to benzaldehyde. Triphenylphosphine is oxidized to triphenylphosphine oxide with a turnover number of >2000 mol.P/mol.cat.

摘要

描述了一种带有末端N,N',N"-三甲基-1,4,7-三氮杂环壬烷（Me(3)TACN）配体的空间位阻二（μ-羧基）二铁（II）配合物的合成及其与氧气反应生成（μ-氧代）二（μ-羧基）二铁（III）配合物的过程。这两种化合物均以O(2)作为末端氧化剂引发催化氧转移反应，将膦转化为氧化膦，二甲基硫醚转化为二甲基亚砜，二苄胺转化为苯甲醛。三苯基膦被氧化为三苯基氧化膦，周转数>2000 mol.P/mol.cat。