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4‑Butadiene)Sn(0) Complexes: A New Approach for Zero-Valent p‑Block Elements Utilizing a Butadiene as a 4π-Electron Donor

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posted on 11.08.2016, 00:00 by Takuya Kuwabara, Marisa Nakada, Jumpei Hamada, Jing Dong Guo, Shigeru Nagase, Masaichi Saito
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 η4-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.