Pentamethylcyclopentadienyltrimethylgermane: A Nontoxic Entry to Mid-Valent Monopentamethylcyclopentadienylvanadium Chloride Complexes

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-08-06 DOI:10.1021/acs.organomet.4c00276

Adrián Calvo-Molina, Adrián Pérez-Redondo, Carlos Yélamos

{"title":"Pentamethylcyclopentadienyltrimethylgermane: A Nontoxic Entry to Mid-Valent Monopentamethylcyclopentadienylvanadium Chloride Complexes","authors":"Adrián Calvo-Molina, Adrián Pérez-Redondo, Carlos Yélamos","doi":"10.1021/acs.organomet.4c00276","DOIUrl":null,"url":null,"abstract":"The reaction of [VCl3(thf)3] with [Ge(C5Me5)Me3] provides an efficient and nontoxic alternative synthesis for the vanadium(III) trimer [{VCp*(μ-Cl)2}3] (Cp* = η5-C5Me5) (1). The trinuclear structure of 1 is preserved in aromatic hydrocarbon solvents and can be easily oxidized with [FeCp2](BPh4) to give [{VCp*(μ-Cl)2}3](BPh4). In contrast, 1 undergoes dissociation in coordinating solvents to form mononuclear species [VCp*Cl2(L)] (L = thf, py), which can be reduced with magnesium to afford dinuclear mixed-valence V(III)/V(II) [(VCp*)2(μ-Cl)3] or V(II) [{VCp*(py)(μ-Cl)}2] derivatives. The latter compound reduces in two electrons the N═N bond of azobenzene at room temperature to give the vanadium(III) derivative [{VCp*(μ-Cl)}2(μ–η2:η2-N2Ph2)], which undergoes cleavage of the N–N bond at 90 °C to form the imido-bridged dinuclear vanadium(IV) complex [{VCp*Cl(μ-NPh)}2].","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00276","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

The reaction of [VCl₃(thf)₃] with [Ge(C₅Me₅)Me₃] provides an efficient and nontoxic alternative synthesis for the vanadium(III) trimer [{VCp*(μ-Cl)₂}₃] (Cp* = η⁵-C₅Me₅) (1). The trinuclear structure of 1 is preserved in aromatic hydrocarbon solvents and can be easily oxidized with [FeCp₂](BPh₄) to give [{VCp*(μ-Cl)₂}₃](BPh₄). In contrast, 1 undergoes dissociation in coordinating solvents to form mononuclear species [VCp*Cl₂(L)] (L = thf, py), which can be reduced with magnesium to afford dinuclear mixed-valence V(III)/V(II) [(VCp*)₂(μ-Cl)₃] or V(II) [{VCp*(py)(μ-Cl)}₂] derivatives. The latter compound reduces in two electrons the N═N bond of azobenzene at room temperature to give the vanadium(III) derivative [{VCp*(μ-Cl)}₂(μ–η²:η²-N₂Ph₂)], which undergoes cleavage of the N–N bond at 90 °C to form the imido-bridged dinuclear vanadium(IV) complex [{VCp*Cl(μ-NPh)}₂].

Abstract Image

查看原文本刊更多论文

五甲基环戊二烯三甲基锗：五甲基环戊二烯基三甲基锗：中价单五甲基环戊二烯基氯化钒络合物的无毒入口

VCl3(thf)3]与[Ge(C5Me5)Me3]的反应为钒(III)三聚体[{VCp*(μ-Cl)2}3]（Cp* = η5-C5Me5）(1)提供了一种高效、无毒的替代合成方法。1 的三核结构在芳香烃溶剂中得以保留，并且很容易被 [FeCp2](BPh4)氧化，生成 [{VCp*(μ-Cl)2}3](BPh4)。相反，1 在配位溶剂中发生解离，形成单核物种 [VCp*Cl2(L)] （L = thf，py），可与镁还原生成双核混价 V(III)/V(II) [(VCp*)2(μ-Cl)3]或 V(II) [{VCp*(py)(μ-Cl)}2] 衍生物。后一种化合物在室温下以两个电子还原偶氮苯的 N═N键，生成钒（III）衍生物[{VCp*（μ-Cl）}2（μ-η2:η2-N2Ph2）]，该衍生物在 90 °C时发生 N-N 键裂解，生成酰亚胺桥接的双核钒（IV）配合物[{VCp*Cl（μ-NPh）}2]。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.