Diversity-oriented functionalization of silanes via ruthenium phthalocyanine-catalyzed carbene Si-H insertion

Abstract

carbene Si-H insertion catalyzed by the ruthenium(II) phthalocyanine complex. A broad range of primary, secondary, and tertiary silanes bearing aromatic, aliphatic, and alkylaromatic substituents undergo smooth insertion with various diazo compounds as carbene precursors, affording single insertion products in good to excellent yields (61-100%) with turnover numbers up to 15 400. The method enables selective stepwise introduction of two different carbene fragments into silanes and disilanes, providing access to non-symmetrical derivatives, a transformation not previously reported. Mechanistic studies, including kinetic isotope effects and DFT calculations, reveal an asynchronous concerted mechanism with rate-limiting Si-H bond cleavage. This work expands the synthetic utility of phthalocyanine catalysts for preparing elaborated organosilanes.

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BibTeX

@article{toullec2026diversityoriented,
  title = {{Diversity-oriented functionalization of silanes via ruthenium phthalocyanine-catalyzed carbene Si-H insertion}},
  author = {C. Toullec and A. Kroitor and L. Demina and A. Martynov and Y. Gorbunova and A. Sorokin},
  journal = {Dalton Transactions},
  year = {2026},
  month = oct,
  doi = {10.1039/d6dt01671e},
  url = {https://hal.science/hal-05777786v1},
  note = {CC BY-NC},
}

RIS

TY  - JOUR
TI  - Diversity-oriented functionalization of silanes via ruthenium phthalocyanine-catalyzed carbene Si-H insertion
AU  - C. Toullec
AU  - A. Kroitor
AU  - L. Demina
AU  - A. Martynov
AU  - Y. Gorbunova
AU  - A. Sorokin
PY  - 2026
DA  - 2026/10/05
JO  - Dalton Transactions
DO  - 10.1039/d6dt01671e
UR  - https://hal.science/hal-05777786v1
AB  - carbene Si-H insertion catalyzed by the ruthenium(II) phthalocyanine complex. A broad range of primary, secondary, and tertiary silanes bearing aromatic, aliphatic, and alkylaromatic substituents undergo smooth insertion with various diazo compounds as carbene precursors, affording single insertion products in good to excellent yields (61-100%) with turnover numbers up to 15 400. The method enables selective stepwise introduction of two different carbene fragments into silanes and disilanes, providing access to non-symmetrical derivatives, a transformation not previously reported. Mechanistic studies, including kinetic isotope effects and DFT calculations, reveal an asynchronous concerted mechanism with rate-limiting Si-H bond cleavage. This work expands the synthetic utility of phthalocyanine catalysts for preparing elaborated organosilanes.
SN  - 1477-9226
SN  - 1477-9234
ER  -

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