Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand
| Autor: | Akseli Mansikkamäki, Heikki M. Tuononen, Paul Chuk-Yan Hui, Vladimir K. Michaelis, Guy M. Bernard, Roderick E. Wasylishen, Chris Gendy, Joshua Heidebrecht, Roland Roesler, Juuso Valjus |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_element
Bite angle organometalliyhdisteet 010402 general chemistry 01 natural sciences Catalysis Transmetalation chemistry.chemical_compound nickel Polymer chemistry Moiety Chelation Lewis acids and bases N-heterocyclic carbenes ta116 010405 organic chemistry Ligand General Medicine General Chemistry kompleksiyhdisteet 0104 chemical sciences T-geometry Nickel germanium metal-only Lewis pairs chemistry nikkeli Derivative (chemistry) |
| Zdroj: | Angewandte Chemie International Edition. 58(1):154-158 |
| ISSN: | 1433-7851 |
| Popis: | Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η 2 -cod), 3. In reaction with GeCl2, this produced (2)NiGeCl2, 4, featuring a T-shaped Ni(0) and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2, in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2Ni(cod) complexes 9 and 10, as well as (NHC)2GeCl2 derivative 11, incorporating ligands that cannot accommodate a wide bite angle, failed to produce isolable Ni-Ge complexes. The isolation of (2)Ni(η 2 -Py), 12, provides further evidence for the reluctance of the (2)Ni(0) fragment to act as a σLewis acid. peerReviewed |
| Databáze: | OpenAIRE |
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