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由阴离子三（膦基）硼酸酯配体[PhBP(iPr)3]支撑的假四面体锰配合物。

Pseudotetrahedral manganese complexes supported by the anionic tris(phosphino)borate ligand [PhBP(iPr)3].

作者信息

Lu Connie C, Peters Jonas C

机构信息

Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.

出版信息

Inorg Chem. 2006 Oct 16;45(21):8597-607. doi: 10.1021/ic060735q.

DOI:10.1021/ic060735q
PMID:17029370
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2920598/
Abstract

This paper presents aspects of the coordination chemistry of mono- and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand, [PhBP(i)(Pr)3] (where [PhBP(i)(Pr)3] = [PhB(CH(2)P(i)Pr2)3]-). The Mn(II) halide complexes, [PhBP(i)(Pr)3]MnCl (1) and [PhBP(i)(Pr)3]MnI (2), have been characterized by X-ray diffraction, SQUID magnetometry, and EPR spectroscopy. Compound 2 serves as a precursor to a series of Mn azide, alkyl, and amide species: [PhBP(i)(Pr)3]Mn(N3) (3), [PhBP(i)(Pr)3]Mn(CH2Ph) (4), [PhBP(i)(Pr)3]Mn(Me) (5), [PhBP(i)(Pr)3]Mn(NH(2,6-(i)Pr2-C6H3)) (6), [PhBP(i)(Pr)3]Mn(dbabh) (7), and [PhBP(i)(Pr)3]Mn(1-Ph(isoindolate)) (8). The complexes 2-8 feature a divalent-metal center and are pseudotetrahedral. They collectively represent an uncommon structural motif for low-coordinate, polyphosphine-supported Mn complexes. Two Mn(I) species have also been prepared. These include the Tl-Mn adduct [PhBP(i)(Pr)3]Tl-MnBr(CO)4 (9) and the octahedral complex [PhBP(i)(Pr)3]Mn(CN(t)Bu)3 (10). Some of our initial synthetic efforts to generate [PhBP(i)(Pr)3]MnN(x) species are briefly described, as are DFT studies that probe the electronic viability of these types of multiply bonded target structures.

摘要

本文介绍了由阴离子三（膦基）硼酸盐配体[PhBP(i)(Pr)3]（其中[PhBP(i)(Pr)3]=[PhB(CH(2)P(i)Pr2)3]-）支撑的一价和二价锰配合物的配位化学方面。二价锰卤化物配合物[PhBP(i)(Pr)3]MnCl（1）和[PhBP(i)(Pr)3]MnI（2）已通过X射线衍射、超导量子干涉仪磁强计和电子顺磁共振光谱进行了表征。化合物2是一系列叠氮基锰、烷基锰和酰胺基锰物种的前体：[PhBP(i)(Pr)3]Mn(N3)（3）、[PhBP(i)(Pr)3]Mn(CH2Ph)（4）、[PhBP(i)(Pr)3]Mn(Me)（5）、[PhBP(i)(Pr)3]Mn(NH(2,6-(i)Pr2-C6H3))（6）、[PhBP(i)(Pr)3]Mn(dbabh)（7）和[PhBP(i)(Pr)3]Mn(1-Ph(异吲哚酸酯))（8）。配合物2 - 8具有二价金属中心，呈假四面体结构。它们共同代表了低配位、多膦支撑的锰配合物中一种不常见的结构模式。还制备了两种一价锰物种。其中包括铊 - 锰加合物[PhBP(i)(Pr)3]Tl - MnBr(CO)4（9）和八面体配合物[PhBP(i)(Pr)3]Mn(CN(t)Bu)3（10）。简要描述了我们最初生成[PhBP(i)(Pr)3]MnN(x)物种的一些合成尝试，以及探究这些多重键合目标结构类型电子可行性的密度泛函理论研究。

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