{"title":"Monodentate σ-Accepting Boron-Based Ligands Bearing Square-Planar Ni(0) Centers","authors":"Yutaka Mondori, Yasuhiro Yamauchi, Takahiro Kawakita, Sensuke Ogoshi, Yuta Uetake, Yasuo Takeichi, Hidehiro Sakurai, Yoichi Hoshimoto","doi":"10.1021/jacs.4c15892","DOIUrl":null,"url":null,"abstract":"Transition metals are known to work as electron donors toward electron-accepting heavier-group-13 elements (Al, Ga, and In), called Z-type ligands. However, complexes with boron-based Z-type ligands are stable only in the presence of additional coordination units (the so-called “supported-ligand” strategy). Here, we report the synthesis and characterization of square-planar Ni(0) complexes that bear tris(perfluoroaryl)boranes as monodentate Z-type ligands, even though such coordination geometry has been traditionally associated with Ni(II) species based on the well-established ligand-field theory. A combined theoretical and experimental approach revealed a mixed covalent/dative character for the Ni–B bonds. This strategy uses frustrated L/Z-ligand pairs that combine sterically encumbered electron-donating (L-type) and electron-accepting ligands to form noncovalent interactions over L–M–Z units to achieve unprecedented low-valent transition metal species with monodentate Z-type ligands.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"31 1","pages":""},"PeriodicalIF":14.4000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c15892","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Transition metals are known to work as electron donors toward electron-accepting heavier-group-13 elements (Al, Ga, and In), called Z-type ligands. However, complexes with boron-based Z-type ligands are stable only in the presence of additional coordination units (the so-called “supported-ligand” strategy). Here, we report the synthesis and characterization of square-planar Ni(0) complexes that bear tris(perfluoroaryl)boranes as monodentate Z-type ligands, even though such coordination geometry has been traditionally associated with Ni(II) species based on the well-established ligand-field theory. A combined theoretical and experimental approach revealed a mixed covalent/dative character for the Ni–B bonds. This strategy uses frustrated L/Z-ligand pairs that combine sterically encumbered electron-donating (L-type) and electron-accepting ligands to form noncovalent interactions over L–M–Z units to achieve unprecedented low-valent transition metal species with monodentate Z-type ligands.
期刊介绍:
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