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Peer-reviewedCC BY-NC-NDJACS Au

Complete Isocyanide Triple Bond Scission by a Silylene Yields an Optoelectronic 1,3-Disilacyclobutene.

  • Pratiksha B Ghanwat1,2
  • Rinu Pandya2,3
  • A Aparna1,2
  • Arindam Biswas2,3
  • Kumar Vanka2,3
  • Arup K Rath2,3
  • Sakya S Sen1,2
  1. 1Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.
  2. 2Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India.
  3. 3Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.
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Abstract

The complete scission of strong triple bonds is a definitive hallmark of transition metals, typically remaining beyond the reach of main-group elements. Despite the success of silylenes in activating various inert linkages, the full fragmentation of the isocyanide CN moiety by a low-valent silicon center has yet to be realized. Herein, we report that the hypersilyl-stabilized amidinato-silylene, [PhC-(NtBu)2SiSi-(SiMe3)3] (1), accomplishes the complete cleavage of the CN triple bond in xylyl and mesityl isocyanides, providing a new benchmark for silicon-mediated small-molecule activation. We also demonstrate remarkably divergent reactivity where the isocyanide substituent dictates the product formation: aryl isocyanides undergo a complex multistep rearrangement and simultaneous CN and Si-Si bond scission to yield novel cyclic silenes (2 and 3) in high yield, whereas cyclohexyl isocyanide leads to a stable insertion product (4) keeping the oxidation state of silicon intact. Such an insertion reaction contrasts with common reports on the reactivity of low-valent silicon compounds, which are regularly oxidized to a more stable higher oxidation state. Finally, we reveal the successful integration of the cyclic silene 2 as a hole-injection layer in a functional light-emitting diode device.

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Cite

BibTeXRIS
BibTeX
@article{ghanwat2026complete,
  title = {{Complete Isocyanide Triple Bond Scission by a Silylene Yields an Optoelectronic 1,3-Disilacyclobutene.}},
  author = {Pratiksha B Ghanwat and Rinu Pandya and A Aparna and Arindam Biswas and Kumar Vanka and Arup K Rath and Sakya S Sen},
  journal = {JACS Au},
  year = {2026},
  month = sep,
  doi = {10.1021/jacsau.6c00950},
  url = {https://europepmc.org/article/MED/42953616},
  note = {CC BY-NC-ND},
}
RIS
TY  - JOUR
TI  - Complete Isocyanide Triple Bond Scission by a Silylene Yields an Optoelectronic 1,3-Disilacyclobutene.
AU  - Pratiksha B Ghanwat
AU  - Rinu Pandya
AU  - A Aparna
AU  - Arindam Biswas
AU  - Kumar Vanka
AU  - Arup K Rath
AU  - Sakya S Sen
PY  - 2026
DA  - 2026/09/25
JO  - JACS Au
DO  - 10.1021/jacsau.6c00950
UR  - https://europepmc.org/article/MED/42953616
AB  - The complete scission of strong triple bonds is a definitive hallmark of transition metals, typically remaining beyond the reach of main-group elements. Despite the success of silylenes in activating various inert linkages, the full fragmentation of the isocyanide CN moiety by a low-valent silicon center has yet to be realized. Herein, we report that the hypersilyl-stabilized amidinato-silylene, [PhC-(NtBu)2SiSi-(SiMe3)3] (1), accomplishes the complete cleavage of the CN triple bond in xylyl and mesityl isocyanides, providing a new benchmark for silicon-mediated small-molecule activation. We also demonstrate remarkably divergent reactivity where the isocyanide substituent dictates the product formation: aryl isocyanides undergo a complex multistep rearrangement and simultaneous CN and Si-Si bond scission to yield novel cyclic silenes (2 and 3) in high yield, whereas cyclohexyl isocyanide leads to a stable insertion product (4) keeping the oxidation state of silicon intact. Such an insertion reaction contrasts with common reports on the reactivity of low-valent silicon compounds, which are regularly oxidized to a more stable higher oxidation state. Finally, we reveal the successful integration of the cyclic silene 2 as a hole-injection layer in a functional light-emitting diode device.
SN  - 2691-3704
ER  -