Thermal Reactions of Fullerenes with Cyclic Organosilicon and Organogermanium Compounds: Silylation and Germylation of C<sub>60</sub> and C<sub>70</sub>

Kako, Masahiro; Inaba, Daiki; Minami, Kazuya; Iida, Ryosuke; Nakahodo, Tsukasa; Akasaka, Takeshi

doi:10.1002/hc.21230

Cited by 5 publications

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“…Recent progress has revealed that the chemical reactivity of EMFs differs greatly from that of empty fullerenes and that it is strongly dependent on the encaged metal species. For instance, M@ C 2 v (9)-C 82 (M = La, Ce, Pr, Gd, and Y) and M 2 @ I h (7)-C 80 (M = La and Ce) undergo both photochemical and thermal reactions with disilirane to form bis-silylated adducts, whereas the reactions of empty fullerenes (C 60 , C 70 , C 76 , and D 2 (22)-C 84 ) and Sc 3 N@ I h (7)-C 80 with disilirane are suppressed under thermal conditions . Akasaka et al reported that retro-reaction of a Diels–Alder adduct, La@ C 2 v (9)-C 82 (Cp) (Cp = cyclopentadiene), proceeded much faster than that of C 60 (Cp) .…”

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D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine

et al. 2016

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We compared the chemical reactivity of D(23)-C and that of ScC@D(23)-C, both having the same carbon cage geometry, in the photolysis of 2-adamantane-2,3'-[3H]-diazirine, to clarify metal-atom doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies have revealed that the chemical reactivity of the D(23)-C carbon cage is altered drastically by endohedral ScC doping. The reaction of empty D(23)-C with the diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR spectroscopic studies revealed that the major Ad monoadduct (C(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C(Ad)-B) has a methanofullerene structure. The latter was also characterized using X-ray crystallography. C(Ad)-A is stable under photoirradiation, but it interconverted to C(Ad)-B by heating at 80 °C. In contrast, the reaction of endohedral ScC@D(23)-C with diazirine under photoirradiation affords four Ad monoadducts (ScC@C(Ad)-A, ScC@C(Ad)-B, ScC@C(Ad)-C, and ScC@C(Ad)-D). The structure of ScC@C(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of ScC@C(Ad)-A and ScC@C(Ad)-B to ScC@C(Ad)-C was also observed. The reaction mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations. Calculation results suggest that C(Ad)-B and ScC@C(Ad)-C are thermodynamically favorable products. Their different chemical reactivities derive from ScC doping, which raises the HOMO and LUMO levels of the D(23)-C carbon cage.

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Section: Introductionmentioning

confidence: 99%

D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine

et al. 2016

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“…1a) 9 as do low-valent silicon and germanium surrogates under photolytic or high temperature conditions. 10…”

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A molecular aluminium fulleride

et al. 2023

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Organogermanium Compounds of the Main Group Elements

Zaitsev¹

2023

Organogermanium Compounds

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Thermal Reactions of Fullerenes with Cyclic Organosilicon and Organogermanium Compounds: Silylation and Germylation of C₆₀ and C₇₀

Cited by 5 publications

References 36 publications

D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine

D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine

A molecular aluminium fulleride

Organogermanium Compounds of the Main Group Elements

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Thermal Reactions of Fullerenes with Cyclic Organosilicon and Organogermanium Compounds: Silylation and Germylation of C60 and C70

Cited by 5 publications

References 36 publications

D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical Reactivity in the Photolysis of Diazirine

D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical Reactivity in the Photolysis of Diazirine

A molecular aluminium fulleride

Organogermanium Compounds of the Main Group Elements

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Thermal Reactions of Fullerenes with Cyclic Organosilicon and Organogermanium Compounds: Silylation and Germylation of C₆₀ and C₇₀

D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine

D_2d(23)-C₈₄ versus Sc₂C₂@D_2d(23)-C₈₄: Impact of Endohedral Sc₂C₂ Doping on Chemical Reactivity in the Photolysis of Diazirine