S‐Heterocyclic Carbene with a Disilane Backbone

Nikawa, Hidefumi; Nakahodo, Tsukasa; Tsuchiya, Takahiro; Wakahara, Takatsugu; Rahman, Gul; Akasaka, Takeshi; Maeda, Yutaka; Liu, Michael T. H.; Meguro, Akira; Kyushin, Soichiro; Matsumoto, Hideyuki; Mizorogi, Naomi; Nagase, Shigeru

doi:10.1002/anie.200502971

Cited by 25 publications

(6 citation statements)

References 44 publications

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“…On the basis of these data, we propose that the reaction between C 60 and IDipp provides IDipp–C 60 as shown in Scheme . These results contrast with previously observed reactivity with smaller carbenes, which yield cyclopropane species. , …”

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confidence: 99%

Fullerene–Carbene Lewis Acid–Base Adducts

Risko

Seo

et al. 2011

J. Am. Chem. Soc.

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The reaction between a bulky N-heterocylic carbene (NHC) and C(60) leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths similar to those of n-doped fullerenes were observed for the product, consistent with a net transfer of electron density to the C(60) core. Corroborating information was obtained using UV photoelectron spectroscopy, which revealed that the adduct has an ionization potential ∼1.5 eV lower than that of C(60). Density functional theory calculations showed that the C-C bond is polarized, with a total charge of +0.84e located on the NHC framework and -0.84e delocalized on the C(60) cage. The combination of reactivity, characterization, and theoretical studies demonstrates that fullerenes can behave as Lewis acids that react with C-based Lewis bases and that the overall process describes n-doping via C-C bond formation.

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confidence: 99%

Fullerene–Carbene Lewis Acid–Base Adducts

Risko

Seo

et al. 2011

J. Am. Chem. Soc.

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“…Driess et al reported a new cooperative activation of CS 2 by bridged bis( N -heterocyclic silylenes), resulting in the dearomatization of an intramolecular bridging benzene ring (Scheme a) . As depicted in Scheme b, the [3+2] cycloaddition reaction of disilenes with CS 2 generated S-heterocyclic carbenes . N-Heterocyclic diazoolefins featuring a terminal N 2 group reacted readily with carbon disulfide to afford a [3+2] cycloaddition product in high yield (Scheme c) .…”

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confidence: 99%

Activation of CS₂ with the 2H-Phosphindole Complex to Construct P,S-Polycycles

et al. 2022

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The activation of CS 2 by the 2H-phosphindole complex with a low-coordinate phosphadiene moiety is reported. The successive hetero-Diels− Alder reaction between 2H-phosphindoles and CS 2 constructs two bridged rings and one spirocycle simultaneously, affording structurally complex P,Spolycyclic products. The two 2H-phosphindoles approach the C�S bond in a head-to-head disposition to minimize steric hindrance. This work reveals the unique reactivity of low-coordinate organophosphorus species and their potential applications in small molecule activation.

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“…The cyclotetrasilenes 565a and 565b can also be generated as intermediates in the photolysis of the tricyclic ladder oligosilanes ( 564a and 564b ) and trapped by cycloaddition between the SiSi π-manifold and 2,3-dimethylbutadiene (Scheme ) . Using a similar procedure, the in situ generated cyclotetrasilene 565a combines with CS 2 to form a transient S -heterocyclic carbene that attacks C 60 to form the addition product 566 (Scheme ) …”

Section: Inorganic Rings Derived From Group 12–17 Elementsmentioning

confidence: 99%