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Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes
Author(s) -
Saito Masaichi,
Akiba Tomoki,
Kaneko Misumi,
Kawamura Toshiaki,
Abe Minori,
Hada Masahiko,
Minoura Mao
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201303672
Subject(s) - adduct , chemistry , pyridine , dimer , hypervalent molecule , carbene , divalent , reactivity (psychology) , medicinal chemistry , lewis acids and bases , electrophile , benzene , atom (system on chip) , base (topology) , tetrahydrofuran , stereochemistry , crystallography , organic chemistry , catalysis , medicine , alternative medicine , pathology , reagent , mathematical analysis , mathematics , solvent , computer science , embedded system
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.