由多齿[N2P2]配体支撑的锰和铁配合物的合成与表征。

Synthesis and characterization of manganese and iron complexes supported by multidentate [N2P2] ligands.

作者信息

Chomitz Wayne A, Arnold John

机构信息

Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA.

出版信息

Dalton Trans. 2009 Mar 14(10):1714-20. doi: 10.1039/b821954k. Epub 2009 Jan 26.

DOI:10.1039/b821954k

PMID:19240904

Abstract

The coordination chemistry of mono- and divalent manganese and iron complexes supported by the monoanionic multidentate ligands, [N2P2] (where [N2P2] = tBuN(-)SiMe2N(CH2CH2PiPr2)2) and [N2P2tolyl] (where [N2P2 tolyl] = MeC6H4N(-)SiMe2(CH2CH2PiPr2)2) is presented. The Mn(II) and Fe(II) halide complexes [N2P2]MnCl (1) and [N2P2]FeCl (2) serve as precursors to the alkyl and hydride species [N2P2]MnMe (3), [N2P2]FeMe (4), [N2P2]FeCH2SiMe3 (5), and ([N2P2]Mn)2(mu-H)2 (6). Reduction of 1 and 2 results in the formation of the new bridging dinitrogen complexes ([N2P2]Mn)2(mu-N2) (7) and ([N2P2]Fe)2(mu-N2) (8), respectively. Upon exposure to vacuum, N2 is abstracted from 8, resulting in the observed Fe(I) complex, [N2P2]Fe (9). The new Fe(II) halide complex [N2P2tolyl]FeCl (10) was isolated following the substitution of [N2P2tolyl] for [N2P2]. Reduction of 10 in the presence of N2 resulted in the formation of the dinitrogen free adduct [N2P2tolyl]Fe (11).

摘要

本文介绍了由单阴离子多齿配体[N2P2]（其中[N2P2]=tBuN(-)SiMe2N(CH2CH2PiPr2)2）和[N2P2tolyl]（其中[N2P2tolyl]=MeC6H4N(-)SiMe2(CH2CH2PiPr2)2）支撑的一价和二价锰及铁配合物的配位化学。锰（II）和铁（II）卤化物配合物[N2P2]MnCl（1）和[N2P2]FeCl（2）可作为烷基和氢化物物种[N2P2]MnMe（3）、[N2P2]FeMe（4）、[N2P2]FeCH2SiMe3（5）和([N2P2]Mn)2(μ-H)2（6）的前体。1和2的还原分别导致形成新的桥连二氮配合物([N2P2]Mn)2(μ-N2)（7）和([N2P2]Fe)2(μ-N2)（8）。暴露于真空时，N2从8中被提取出来，得到观察到的铁（I）配合物[N2P2]Fe（9）。用[N2P2tolyl]取代[N2P2]后，分离得到新的铁（II）卤化物配合物[N2P2tolyl]FeCl（10）。在N2存在下10的还原导致形成无二氮加合物[N2P2tolyl]Fe（11）。