Research on zero-valent p-block elements is a recent hot topic in synthetic and theoretical chemistry because of their novel electronic states having two lone pairs in both the s- and p-orbitals. It is considered that σ-donating ligands bearing large substituents are essential to stabilize these species. Herein, we propose a new approach using butadiene as a 4π-electron donor to stabilize zero-valent group 14 elements. During our study to explore the coordination chemistry of stannacyclopentadienyl ligands, unexpected products, in which the tin atom is coordinated by a butadiene in a η(4)-fashion, were obtained. Because butadiene is a neutral 4π-electron donating ligand, the formal oxidation number of the tin atoms of the products should be zero, which is supported by X-ray diffraction analysis and theoretical calculations. A mechanism for the formation of the products is also described.
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http://dx.doi.org/10.1021/jacs.6b07304 | DOI Listing |
Angew Chem Int Ed Engl
August 2017
Department de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona, Martí i Franquès, 1-11, 08028, Barcelona, Spain.
While double bonds are known for transition metals of Groups 9 and 10 as well as for boron and p-block elements of Groups 14-16, Zn sits in a small region of the periodic table with no well-characterized double bonds. A qualitative reasoning indicates that zero-valent zinc has the potential to form Zn=Zn double bonds. A computational study in search for complexes that might showcase this new bond type is presented here.
View Article and Find Full Text PDFJ Am Chem Soc
September 2016
Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama 338-8570, Japan.
Research on zero-valent p-block elements is a recent hot topic in synthetic and theoretical chemistry because of their novel electronic states having two lone pairs in both the s- and p-orbitals. It is considered that σ-donating ligands bearing large substituents are essential to stabilize these species. Herein, we propose a new approach using butadiene as a 4π-electron donor to stabilize zero-valent group 14 elements.
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