Academic Journal
Unmasking the constitution and bonding of the proposed lithium nickelate “Li 3 NiPh 3 (solv) 3 ”: revealing the hidden C 6 H 4 ligand
| العنوان: | Unmasking the constitution and bonding of the proposed lithium nickelate “Li 3 NiPh 3 (solv) 3 ”: revealing the hidden C 6 H 4 ligand |
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| المؤلفون: | Somerville, Rosie J., Borys, Andryj M., Perez-Jimenez, Marina, Nova, Ainara, Balcells, David, Malaspina, Lorraine A., Grabowsky, Simon, Carmona, Ernesto, Hevia, Eva, Campos, Jesús |
| المصدر: | Somerville, Rosie J.; Borys, Andryj M.; Perez-Jimenez, Marina; Nova, Ainara; Balcells, David; Malaspina, Lorraine A.; Grabowsky, Simon; Carmona, Ernesto; Hevia, Eva; Campos, Jesús (2022). Unmasking the constitution and bonding of the proposed lithium nickelate “Li 3 NiPh 3 (solv) 3 ”: revealing the hidden C 6 H 4 ligand. Chemical Science, 13(18), pp. 5268-5276. The Royal Society of Chemistry 10.1039/d2sc01244h |
| بيانات النشر: | The Royal Society of Chemistry |
| سنة النشر: | 2022 |
| المجموعة: | BORIS (Bern Open Repository and Information System, University of Bern) |
| مصطلحات موضوعية: | 570 Life sciences, biology, 540 Chemistry, 000 Computer science, knowledge & systems |
| الوصف: | More than four decades ago, a complex identified as the planar homoleptic lithium nickelate “Li3 NiPh3(solv)3” was reported by Taube and co-workers. This and subsequent reports involving this complex have lain dormant since; however, the absence of an X-ray diffraction structure leaves questions as to the nature of the Ni–PhLi bonding and the coordination geometry at Ni. By systematically evaluating the reactivity of Ni(COD)2 with PhLi under different conditions, we have found that this classical molecule is instead a unique octanuclear complex, [{Li3(solv) 2Ph3Ni}2(m-h2 :h2 -C 6H4 )] (5). This is supported by X-ray crystallography and solution-state NMR studies. A theoretical bonding analysis from NBO, QTAIM, and ELI perspectives reveals extreme back-bonding to the bridging C 6H4 ligand resulting in dimetallabicyclobutane character, the lack of a Ni–Ni bond, and pronounced s-bonding between the phenyl carbanions and nickel, including a weak sC–Li / sNi interaction with the C–Li bond acting as a s-donor. Employing PhNa led to the isolation of [Na2 (solv)3Ph2NiCOD]2 (7) and [Na2(solv)3 Ph2(NaC8H11 )Ni(COD)]2 (8), which lack the benzyne-derived ligand. These findings provide new insights into the synthesis, structure, bonding and reactivity of heterobimetallic nickelates, whose prevalence in organonickel chemistry and catalysis is likely greater than previously believed. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | application/pdf |
| اللغة: | English |
| Relation: | https://boris.unibe.ch/176065/ |
| الاتاحة: | https://boris.unibe.ch/176065/1/d2sc01244h.pdf https://boris.unibe.ch/176065/ |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.5CAD4279 |
| قاعدة البيانات: | BASE |
| الوصف غير متاح. |