Synthesis,Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes |
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| Authors: | Prof. Dr. Masaichi Saito Tomoki Akiba Misumi Kaneko Toshiaki Kawamura Dr. Minori Abe Prof. Dr. Masahiko Hada Prof. Dr. Mao Minoura |
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| Affiliation: | 1. Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo‐okubo, Sakura‐ku, Saitama, 338‐8570 (Japan), Fax: (+81)?48‐858‐3700 http://www.chem.saitama‐u.ac.jp/msaito‐lab/English/indexEng.html;2. Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1‐1 Minami‐Osawa, Hachi‐Oji, Tokyo 192‐0397 (Japan);3. JST, CREST, 4‐1‐8 Honcho, Kawaguchi, Saitama 332‐0012 (Japan);4. Department of Chemistry, College of Science, Rikkyo University, 3‐34‐1 Nishi‐Ikebukuro, Toshima‐ku, Tokyo, 171‐8501 (Japan) |
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| Abstract: | Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine and N‐heterocyclic carbene, were synthesized and characterized. The THF‐ and pyridine‐stabilized compounds can be regarded as rare examples of hypervalent 10‐X‐4 species. The equilibrium between the THF adduct and the free plumbacyclopentadienylidene was evidenced by spectroscopic analysis and theoretical calculations. The THF adduct in benzene converted into a plumbylene dimer, where one of the lead centers is coordinated by THF and the other lead atom is coordinated by a divalent lead atom, the dimer gradually decomposing into spiroplumbole. The THF adduct unexpectedly reacted with trifluoroborane and trichlorogallane to afford fluoroborole and chlorogallole, which are the first examples of non‐annulated fluoroborole and gallole, respectively. |
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| Keywords: | boron gallium Lewis bases lead relativistic effects |
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