Reactions of Titanium- and Zirconium-Based 1-Metallacyclobuta-2,3-diene Complexes with Diazenes: N═N Bond Cleavage versus N–C Bond Formation and Dearomatization

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-06-18 DOI:10.1021/acs.organomet.4c0014210.1021/acs.organomet.4c00142

Sihan Li, Mirjam Schröder, Xinzhe Shi, Anke Spannenberg, Jörg Fischer, Björn Corzilius, Fabian Reiß* and Torsten Beweries*,

{"title":"Reactions of Titanium- and Zirconium-Based 1-Metallacyclobuta-2,3-diene Complexes with Diazenes: N═N Bond Cleavage versus N–C Bond Formation and Dearomatization","authors":"Sihan Li, Mirjam Schröder, Xinzhe Shi, Anke Spannenberg, Jörg Fischer, Björn Corzilius, Fabian Reiß* and Torsten Beweries*, ","doi":"10.1021/acs.organomet.4c0014210.1021/acs.organomet.4c00142","DOIUrl":null,"url":null,"abstract":"The reactions of two [rac-(ebthi)Ti]- and [rac-(ebi)Zr]-based 1-metallacyclobuta-2,3-diene complexes with diazenes are described. With azobenzene, cleavage of the N═N bond is observed in the case of Zr, leading to the formation of dinuclear Zr(IV) imido complex 1. In contrast, the insertion of azobenzene into the Ti–C bond of the titanacycle produces six-membered aza-metallacycle 6, which could only be characterized by nuclear magnetic resonance spectroscopy. With geometrically restricted benzo[c]cinnoline, activation and dearomatization of the phenyl group of the substrate occur, leading to the formation of unusual mononuclear [M = Zr (3)] and dinuclear complexes [M = Ti (7)]. Reaction mechanisms leading to the formation of these unusual complexes are proposed on the basis of control experiments.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 24","pages":"3153–3162 3153–3162"},"PeriodicalIF":2.9000,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00142","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00142","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 reactions of two [rac-(ebthi)Ti]- and [rac-(ebi)Zr]-based 1-metallacyclobuta-2,3-diene complexes with diazenes are described. With azobenzene, cleavage of the N═N bond is observed in the case of Zr, leading to the formation of dinuclear Zr(IV) imido complex 1. In contrast, the insertion of azobenzene into the Ti–C bond of the titanacycle produces six-membered aza-metallacycle 6, which could only be characterized by nuclear magnetic resonance spectroscopy. With geometrically restricted benzo[c]cinnoline, activation and dearomatization of the phenyl group of the substrate occur, leading to the formation of unusual mononuclear [M = Zr (3)] and dinuclear complexes [M = Ti (7)]. Reaction mechanisms leading to the formation of these unusual complexes are proposed on the basis of control experiments.

查看原文本刊更多论文

钛基和锆基1-金属环丁基-2,3-二烯配合物与二氮烯的反应：N = N键断裂与N - c键形成和脱芳构化

报道了两种[rac-(ethi)Ti]-和[rac-(ebi)Zr]基1-金属环丁酸-2,3-二烯配合物与二氮烯的反应。在偶氮苯的情况下，观察到Zr的N = N键断裂，导致形成双核Zr（IV）亚胺配合物1。相比之下，偶氮苯插入钛环的Ti-C键产生六元氮杂金属环6，只能通过核磁共振波谱来表征。在几何受限的苯并[c]肉桂碱中，底物的苯基发生活化和去芳构化，导致形成罕见的单核配合物[M = Zr(3)]和双核配合物[M = Ti(7)]。在对照实验的基础上，提出了导致这些不寻常配合物形成的反应机理。

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.