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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
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AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c10467
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A novel nontransient acyclic iminosilylene compound with a bulky super silyl group and a methylated backbone was isolated. This compound shows intermolecular Bu''chner-ring-expansion-type reactivity, forming silicon analogs of cycloheptatrienes. The reactions with N-heteroarenes are faster and irreversible, resulting in azasilepins with nearly planar seven-membered rings.
A novel nontransient acyclic iminosilylene (1), bearing a bulky super silyl group (-SitBu3) and N-heterocyclic imine ligand with a methylated backbone, was prepared and isolated. The methylated backbone is the feature of 1 that distinguishes it from the previously reported nonisolable iminosilylenes, as it prevents the intramolecular silylene center insertion into an aromatic C-C bond of an aryl substituent. Instead, 1 exhibits an intermolecular Bu''chner-ring-expansion-type reactivity; the silylene is capable of dearomatization of benzene and its derivatives, giving the corresponding silicon analogs of cycloheptatrienes, i.e. silepins, featuring seven-membered SiC6 rings with nearly planar geometry. The ring expansion reactions of 1 with benzene and 1,4bis(trifluoromethyl)benzene are reversible. Similar reactions of 1 with N-heteroarenes (pyridine and DMAP) proceed more rapidly and irreversibly forming the corresponding azasilepins, also with nearly planar seven-membered SiNC5 rings. DFT calculations reveal an ambiphilic nature of 1 that allows the intermolecular aromatic C-C bond insertion to occur. Additional computational studies, which elucidate the inherent reactivity of 1, the role of the substituent effect, and reaction mechanisms behind the ring expansion transformations, are presented.
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