Johannes Stephan, Raphael Bühler, Fabrizio E. Napoli, Christian Gemel and Roland A. Fischer*,
{"title":"Cooperative Reactivity Induced by All-Gallium Coordination at Nickel","authors":"Johannes Stephan, Raphael Bühler, Fabrizio E. Napoli, Christian Gemel and Roland A. Fischer*, ","doi":"10.1021/acs.inorgchem.5c02296","DOIUrl":null,"url":null,"abstract":"<p >Synergistic effects in mixed-metal complexes can lead to small-molecule activation and intriguing reactivity patterns. Herein, we report the dimerization of acetonitrile to a nacnac-type β-diketiminate ligand at the nickel/gallium complex fragment [Ni(GaCp*)<sub>4</sub>]<sup>2+</sup> (Cp* = η<sup>5</sup>-C<sub>5</sub>(CH<sub>3</sub>)<sub>5</sub>). The coordination of GaCp* to the Ni(II) center leads to strong Lewis acidity at the initially Lewis basic Ga(I) ligand, which resembles an “umpolung” of the Ga center. The electrophilic Ga serves as the site of bond activation. DFT calculations indicate that the proximity of Ni and Ga and a Ga-rich coordination sphere around the Ni atom are essential for facilitating the reaction. Interestingly, we discovered an abnormally large kinetic isotope effect of 28 assigned to proton tunneling.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 30","pages":"15707–15714"},"PeriodicalIF":4.7000,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c02296","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02296","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Synergistic effects in mixed-metal complexes can lead to small-molecule activation and intriguing reactivity patterns. Herein, we report the dimerization of acetonitrile to a nacnac-type β-diketiminate ligand at the nickel/gallium complex fragment [Ni(GaCp*)4]2+ (Cp* = η5-C5(CH3)5). The coordination of GaCp* to the Ni(II) center leads to strong Lewis acidity at the initially Lewis basic Ga(I) ligand, which resembles an “umpolung” of the Ga center. The electrophilic Ga serves as the site of bond activation. DFT calculations indicate that the proximity of Ni and Ga and a Ga-rich coordination sphere around the Ni atom are essential for facilitating the reaction. Interestingly, we discovered an abnormally large kinetic isotope effect of 28 assigned to proton tunneling.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
