The π-Annulated Carbene 1,3-Di-iso-propylbenzimidazolin-2-ylidene (BIiPr) and Its Application in Nickel(0) Chemistry

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-02-25 DOI:10.1021/acs.organomet.5c0001510.1021/acs.organomet.5c00015

Martin S. Luff, Celine S. Corsei and Udo Radius*,

{"title":"The π-Annulated Carbene 1,3-Di-iso-propylbenzimidazolin-2-ylidene (BIiPr) and Its Application in Nickel(0) Chemistry","authors":"Martin S. Luff, Celine S. Corsei and Udo Radius*, ","doi":"10.1021/acs.organomet.5c0001510.1021/acs.organomet.5c00015","DOIUrl":null,"url":null,"abstract":"The stereoelectronic parameters of the π-annulated carbene 1,3-di-iso-propylbenzimidazolin-2-ylidene (BIiPr) were evaluated in this study. The N-iso-propyl substituents and the additional π-backbone of BIiPr lead to a moderate steric bulk, which lies in between that of the backbone unsubstituted carbene IiPr and its backbone methylated congener IiPrMe (IR = 1,3-diorganylimidazolin-2-ylidene; IRMe = 1,3-diorganyl-4,5-dimethylimidazolin-2-ylidene). While the net electron donation properties of BIiPr are slightly lower than those of IiPr and IiPrMe, its π-acidity is significantly higher and lies between that of imidazole-based NHCs and cAACs. These unique stereoelectronic properties led to distinctly different reactivities with Ni(0) reagents in comparison to IiPr and IiPrMe. The reaction of BIiPr with [Ni(COD)2] afforded homoleptic three-coordinated [Ni(BIiPr)3] (1) and the olefin complex [Ni2(BIiPr)4(μ2-(η2:η2)-COD)] (2) only as a side product. The reaction of BIiPr with [Ni(CO)4] yielded [Ni(BIiPr)2(CO)2] (3), which was employed as a starting material for the facile synthesis of the uncapped, NHC-ligated nickel Chini-cluster analog [Ni3(BIiPr)3(μ2-CO)3] (4). This cluster was synthesized from the reaction of 3 with [Ni(COD)2]. These results demonstrate the unique stereoelectronic properties of BIiPr and reveal the influence of small variations of the substitutional pattern of NHCs on the stabilities and reactivities of transition metal complexes.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 5","pages":"691–703 691–703"},"PeriodicalIF":2.5000,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00015","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 stereoelectronic parameters of the π-annulated carbene 1,3-di-iso-propylbenzimidazolin-2-ylidene (BIiPr) were evaluated in this study. The N-iso-propyl substituents and the additional π-backbone of BIiPr lead to a moderate steric bulk, which lies in between that of the backbone unsubstituted carbene IiPr and its backbone methylated congener IiPr^Me (IR = 1,3-diorganylimidazolin-2-ylidene; IR^Me = 1,3-diorganyl-4,5-dimethylimidazolin-2-ylidene). While the net electron donation properties of BIiPr are slightly lower than those of IiPr and IiPr^Me, its π-acidity is significantly higher and lies between that of imidazole-based NHCs and cAACs. These unique stereoelectronic properties led to distinctly different reactivities with Ni(0) reagents in comparison to IiPr and IiPr^Me. The reaction of BIiPr with [Ni(COD)₂] afforded homoleptic three-coordinated [Ni(BIiPr)₃] (1) and the olefin complex [Ni₂(BIiPr)₄(μ²-(η²:η²)-COD)] (2) only as a side product. The reaction of BIiPr with [Ni(CO)₄] yielded [Ni(BIiPr)₂(CO)₂] (3), which was employed as a starting material for the facile synthesis of the uncapped, NHC-ligated nickel Chini-cluster analog [Ni₃(BIiPr)₃(μ²-CO)₃] (4). This cluster was synthesized from the reaction of 3 with [Ni(COD)₂]. These results demonstrate the unique stereoelectronic properties of BIiPr and reveal the influence of small variations of the substitutional pattern of NHCs on the stabilities and reactivities of transition metal complexes.

Abstract Image

查看原文本刊更多论文

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.