A Germanium Isocyanide Complex Featuring (n → π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C-H Bond Activation under Mild Conditions
Brown, Z., Vasko, P., Fettinger, J., Tuononen, H., & Power, P. (2012). A Germanium Isocyanide Complex Featuring (n → π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C-H Bond Activation under Mild Conditions. Journal of the American Chemical Society, 134(9), 4045-4048. https://doi.org/10.1021/ja211874u
Published inJournal of the American Chemical Society
© 2012 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
Reaction of the diarylgermylene Ge(ArMe6)2 [ArMe6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2] with tert-butyl isocyanide gave the Lewis adduct species (ArMe6)2GeCNBut, in which the isocyanide ligand displays a decreased C–N stretching frequency consistent with an n → π* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge–C bonding combination between the lone pair of electrons on the germanium atom and the C–N π* orbital of the isocyanide ligand. The complex undergoes facile C–H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N–But bond.
Publication in research information system
MetadataShow full item record
Showing items with similar title or keywords.
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions Sun, Cunfa; Mammen, Nisha; Kaappa, Sami; Yuan, Peng; Deng, Guocheng; Zhao, Chaowei; Yan, Juanzhu; Malola, Sami; Honkala, Karoliina; Häkkinen, Hannu; Teo, Boon K.; Zheng, Nanfeng (American Chemical Society, 2019)Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated ...
Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand Gendy, Chris; Mansikkamäki, Akseli; Valjus, Juuso; Heidebrecht, Joshua; Hui, Paul Chuk-Yan; Bernard, Guy M.; Tuononen, Heikki; Wasylishen, Roderick E.; Michaelis, Vladimir K.; Roesler, Roland (Wiley‐VCH Verlag, 2019)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) ...
López-Estrada, Omar; Torres-Moreno, Jorge L.; Zuniga-Gutierrez, Bernardo; Calaminici, Patrizia; Malola, Sami; Köster, Andreas M.; Häkkinen, Hannu (Royal Society of Chemistry (RSC), 2022)Understanding the magnetic response of electrons in nanoclusters is essential to interpret their NMR spectra thereby providing guidelines for their synthesis towards various target applications. Here, we consider two copper ...
Ammonia Activation by a Nickel NCN-Pincer Complex featuring a Non-Innocent N-Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium Brown, Rudy M.; Garcia, Javier Borau; Valjus, Juuso; Roberts, Christopher; Tuononen, Heikki; Parvez, Masood; Roesler, Roland (Wiley - VCH Verlag GmbH & Co. KGaA, 2015)A Ni0-NCN pincer complex featuring a six-membered N-heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square-planar ...
Spelling out consequences : conditional constructions as a means to resist proposals in organisational planning process Nissi, Riikka (Sage Publications Ltd., 2016)Organisational planning processes often materialise as a series of meetings, where the future of the organisation is jointly discussed and negotiated as a part of local decision-making sequences. Using conversation and ...