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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Low-Coordinate Monomeric Zinc Hydride Complexes with Encapsulating Dipyrromethene Ligands and Reactivity with B(C_6F_5)_3
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Low-Coordinate Monomeric Zinc Hydride Complexes with Encapsulating Dipyrromethene Ligands and Reactivity with B(C_6F_5)_3

机译：低坐标单体锌氢化物配合物，其用B（C_6F_5）_3包装双甲烯配体和反应性

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摘要

The dipyrromethene (DPM) ligand is the key to isolation of monomeric Zn hydride complexes with tricoordinate zinc centers. A range of RDPM ligands with various substituents in the pole position (1,9-positions) were prepared: R = tBu, adamantyl (Ad), mesityl (Mes), 2,6-diisopropylphenyl (DIPP), 2,4,6-triphenylphenyl (Mes~*), or 9-anthracenyl (Anth). Reaction of the ligands with Et_2Zn gave a series of (~RDPM)ZnEt complexes, which were converted with I_2 to the corresponding (~RDPM)ZnI compounds. The latter reacted by salt metathesis with KN(iPr)HBH_3 to the series of Zn hydride complexes (~RDPM) ZnH. For ligands with the larger Mes~* and Anth substituents, (~RDPM) ZnEt was converted to (~RDPM)ZnOSiPh_3, which after reaction with PhSiH_3 gave the hydrides. While Zn hydride complexes with R = tBu or Ad are dimeric, all complexes with aryl-substituents are monomeric. The aryl groups span a cavity around the metal, blocking dimerization and causing a high-field shift of the 1H NMR signals due to the ASIS effect. Attempted abstraction of the hydride with B(C_6F_5)_3 led to cleavage of the B-C_6F_5 bond.
机译：二吡咯乙烯（DPM）配体是分离具有三配位锌中心的单体氢化锌配合物的关键。制备了一系列在极位（1,9-位）具有各种取代基的RDPM配体：R=tBu、金刚烷基（Ad）、均三甲苯基（Mes）、2,6-二异丙基苯基（DIPP）、2,4,6-三苯基（Mes~*）或9-蒽基（Anth）。配体与Et_2Zn反应生成一系列（~RDPM）ZnEt配合物，它们与I_2转化为相应的（~RDPM）ZnI化合物。后者通过与KN（iPr）HBH_3的盐复分解反应生成一系列锌氢化物配合物（~RDPM）ZnH。对于具有较大Mes~*和Anth取代基的配体，（~RDPM）ZnEt转化为（~RDPM）ZnOSiPh_3，与PhSiH_3反应后生成氢化物。当R=tBu或Ad的锌氢化物配合物是二聚体时，所有带有芳基取代基的配合物都是单体。芳基跨越金属周围的空腔，阻止二聚，并由于ASIS效应导致1H NMR信号的高场位移。试图用B（C_6F_5）_3提取氢化物导致B-C_6F_5键断裂。

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  • 作者

    Gerd Ballmann; Johannes Martin; Jens Langer; Christian F?rber; Sjoerd Harder;

  • 作者单位

    Inorganic and Organometallic Chemistry Friedrich-Alexander-Universit?t Erlangen-Nürnberg Egerlandstra?e 1 91058 Erlangen Germany;

    Inorganic and Organometallic Chemistry Friedrich-Alexander-Universit?t Erlangen-Nürnberg Egerlandstra?e 1 91058 Erlangen Germany;

    Inorganic and Organometallic Chemistry Friedrich-Alexander-Universit?t Erlangen-Nürnberg Egerlandstra?e 1 91058 Erlangen Germany;

    Inorganic and Organometallic Chemistry Friedrich-Alexander-Universit?t Erlangen-Nürnberg Egerlandstra?e 1 91058 Erlangen Germany;

    Inorganic and Organometallic Chemistry Friedrich-Alexander-Universit?t Erlangen-Nürnberg Egerlandstra?e 1 91058 Erlangen Germany;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

    Hydride; Zinc; Dipyrromethene; B(C_6F_5)_3;

    机译：氢化物;锌;偶氮丁烯;B（C_6F_5）_3;

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