A Six‐Coordinate Silicon Dihydride Embedded in a Porphyrin: Enhanced Hydride‐Donor Properties and the Catalyst‐Free Hydrosilylation of CO 2

The catalyst‐free hydrosilylation of CO 2 under mild conditions remains limited. Herein, we report the synthesis, characterization, and reactivity of 5,10,15,20‐tetraphenylporphyrinato(dihydrido)silicon(IV) ( 1 ) as a six‐coordinate silicon dihydride. The Si‐H moiety of 1 reacts with polar double bo...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-12, Vol.26 (68), p.15811-15815
Main Authors: Ishida, Shintaro, Hatakeyama, Takuroh, Nomura, Takuya, Matsumoto, Maiko, Yoshimura, Kimio, Kyushin, Soichiro, Iwamoto, Takeaki
Format: Article
Language:English
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Summary:The catalyst‐free hydrosilylation of CO 2 under mild conditions remains limited. Herein, we report the synthesis, characterization, and reactivity of 5,10,15,20‐tetraphenylporphyrinato(dihydrido)silicon(IV) ( 1 ) as a six‐coordinate silicon dihydride. The Si‐H moiety of 1 reacts with polar double bonds and CO 2 in the absence of a catalyst to afford hydrosilylated products. Combining the hydrosilylation with subsequent transformation furnishes formic acid from CO 2 . Computational studies indicate that the hydride‐donor properties of 1 are exceptionally high for a neutral silicon hydride, and that the direct hydride transfer from silicon to carbon is a pivotal step in the hydrosilylation of CO 2 with 1 .
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202002587