The long-sought carbene-bismuthinidene, (CAAC)Bi(Ph), has been synthesized. Notably, this represents both the first example of a carbene-stabilized subvalent bismuth complex and the extension of the carbene-pnictinidene concept to a non-toxic metallic element (Bi). The bonding has been investigated by single-crystal X-ray diffraction studies and DFT calculations. This report also highlights the hitherto unknown reducing and ligand transfer capability of a beryllium(0) complex.
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http://dx.doi.org/10.1002/chem.201900458 | DOI Listing |
Angew Chem Int Ed Engl
August 2024
Fachbereich Chemie, Philipps-Universität Marburg, 35043, Marburg, Germany.
Attempts to create a novel Mg-Be bond by reaction of [(BDI*)MgNa] with Be[N(SiMe)] failed; BDI*=HC[(tBu)C=N(DIPeP)], DIPeP=2,6-EtC-phenyl. Even at elevated temperatures, no conversion was observed. This is likely caused by strong steric shielding of the Be center.
View Article and Find Full Text PDFChemistry
March 2019
Department of Chemistry, University of Virginia, 409 McCormick Rd./ PO Box 400319, Charlottesville, VA, 22904, USA.
The long-sought carbene-bismuthinidene, (CAAC)Bi(Ph), has been synthesized. Notably, this represents both the first example of a carbene-stabilized subvalent bismuth complex and the extension of the carbene-pnictinidene concept to a non-toxic metallic element (Bi). The bonding has been investigated by single-crystal X-ray diffraction studies and DFT calculations.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2016
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 1, 35032, Marburg, Germany.
A rarely used element: The chemistry of ligand-stabilized complexes in oxidation state zero was recently extended to the s block with the discovery of a Be complex stabilized by a cyclic (alkyl)(amino)carbene. Combined experimental and theoretical studies provided conclusive evidence that the complex contains beryllium(0).
View Article and Find Full Text PDFDalton Trans
April 2013
Department of Chemistry, National Institute of Technology Calicut, Kozhikode, 673 601 Kerala, India.
The electronic structure and reactivity of neutral tricoordinated Be(0) compounds BeL(3), L = CO (1), NHC (2) and PMe(3) (3) are explored by quantum mechanical calculations. These BeL(3) complexes are found to be planar or nearly planar like electron deficient BH3 but isoelectronic with NH3 and possess three L→Be donor-acceptor bonds. The Be atom can be considered as sp(2)-hybridized with a lone pair in the highly diffused 2p(z)-orbital in contrast to the sp(3) hybridization in isoelectronic NH(3).
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