Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand
Gendy, C., Mansikkamäki, A., Valjus, J., Heidebrecht, J., Hui, P. C.-Y., Bernard, G. M., Tuononen, H., Wasylishen, R. E., Michaelis, V. K., & Roesler, R. (2019). Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand. Angewandte Chemie International Edition, 58(1), 154-158. https://doi.org/10.1002/anie.201809889
Published inAngewandte Chemie International Edition
DisciplineEpäorgaaninen ja analyyttinen kemiaNanoscience CenterInorganic and Analytical ChemistryNanoscience Center
© 2019 Wiley‐VCH Verlag GmbH & Co.
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.
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