An isolable germylyne radical with a one-coordinate germanium atom

Wang, Dongmin; Zhai, Cai; Chen, Yizhen; He, Yuhao; Chen, Xiaodan; Wang, Shanle; Zhao, Lili; Frenking, Gernot; Wang, Xinping; Tan, Gengwen

doi:10.1038/s41557-022-01081-1

Cited by 31 publications

(23 citation statements)

References 56 publications

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“…During the preparation of this manuscript, a monomeric non-Gomberg type germanium(I) radical using a sterically hindered ligand was reported (Chart 1b, IV). 14 To produce a stable non-Gomberg type germanium radical, we designed [DipN-PLY]Ge 1 (Chart 2a). We envisioned that a phenalenyl (PLY)-based ligand 15 would have a high thermodynamic stability due to the delocalization of an unpaired electron over six α carbon atoms (Chart 2b), thereby stabilizing the resulting radical 1 (i.e., the resonance form 1-B, Chart 2a).…”

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confidence: 99%

Monovalent Germanium Radical Stabilized by a Phenalenyl Scaffold

Kodama

Uchida

Nakasuji

et al. 2022

Preprint

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A monovalent (Non-Gomberg type) germanium radical 1 stabilized by phenalenyl-based bidentate ligand was synthe-sized. Because of the high thermal stability originating from spin delocalization over the phenalenyl moiety, it was possi-ble to isolate compound 1 in crystalline form by sublimation at ca. 300 °C. ESR spectra, crystallographic analysis, theo-retical calculations, and reactivities with carbon radicals suggest that the spin of 1 is distributed on the phenalenyl moie-ty, while 1 behaves as a germanium-centered radical in its reactions with C2Cl6, PhSSPh, and p-benzoquinone to form Ge−E (E = Cl, S, O) bonds.

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mentioning

confidence: 99%

Monovalent Germanium Radical Stabilized by a Phenalenyl Scaffold

Kodama

Uchida

Nakasuji

et al. 2022

Preprint

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“…To date, only one example of a one-coordinate Ge(I) radical and a few two-coordinate Si(I)- and Ge(I)-based radicals have been reported. The isolated Sn(I) and Pb(I) radicals are even scarcer, , although in situ characterization of an anionic stannylene radical bearing a formal Sn(I) atom dates back to 1995 .…”

Section: Introductionmentioning

confidence: 99%

Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum

et al. 2023

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Due to their intrinsic high reactivity, isolation of heavier analogues of carbynes remains a great challenge. Here, we report the synthesis and characterization of a neutral monosubstituted Sn(I) radical (2) supported by a sterically hindered hydrindacene ligand, which represents the first tin analogue of a free carbyne. Different from all Sn(I/III) species reported thus far, the presence of a sole Sn−C σ bond in 2 renders the remaining two Sn 5p orbitals energetically almost degenerate, of which one is singly occupied and the other is empty. Consequently, its S = 1/2 ground state possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, as evidenced by one component of its g matrix (1.957, 1.896, and 1.578) being considerably less than 2. Consistent with this unique electronic structure, 2 can bind to an N-heterocyclic carbene to afford a neutral two-coordinate Sn(I) radical and initiate a one-electron transfer to benzophenone to furnish a Sn(II)-ketyl radical anion adduct. As a manifestation of its Sn-centered radical nature, 2 reacts with diphenyl diselenide and p-benzoquinone to form Sn−S and Sn−O bonds, respectively.

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“…Main group chemistry has seen a resurgence recently, particularly in regard to the synthesis of new kinetically-stabilized main group hydrides 1,2 and novel species bearing low-oxidation state element centers. 3 As a result of their often small HOMO–LUMO energy gaps, 3 a tetrelenes (ER 2 ; E = group 14 element, R = anionic ligand) can activate and functionalize industrially valuable molecules, such as H 2 , CO, or CO 2 . 2 Furthermore, related group 14 element hydride complexes are competent catalysts for controlled hydride transfer to unsaturated substrates.…”

Section: Introductionmentioning

confidence: 99%