Work

Disilicon‐Mediated Carbon Monoxide Activation: From a 1,2,3‐Trisila‐ to 1,3‐Disilacyclopentadienes with Hypercoordinate λ 4 Si‐λ 3 C Double Bonds

Year: 2024

Type: article

Abstract: The facile reaction of the SiPh 2 ‐bridged bis‐silylene (LSi:) 2 SiPh 2 (L=PhC(NBu t ) 2 ) with diphenylacetylene affords the unprecedented 1,2,3‐trisilacyclopentadiene (LSi) 2 (PhC) 2 SiPh 2 1 with a hypercoordinate λ 4 Si−λ 3 Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N 2 O to form the bicyclic oxygenation product 2 through O‐atom insertion in the Si=Si and Si−Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3‐disilacyclopentadiene 3 , representing the first hypercoordinate example of a cyclosilene with a λ 4 Si‐λ 3 C double bond. Likewise, reaction of Xyl‐NC (Xyl=2,6‐dimethylphenyl), an isocyanide isoelectronic with CO, with 1 furnishes the related 1,3‐disilacyclopentadiene 4 but with an amidinato silylene pendent attached to the Si=C carbon ring atom.

Source: Angewandte Chemie

DOI: 10.1002/ange.202414696

Authors: Shenglai Yao, Markus Stefan Budde, Xing Yang, Yun Xiong, Lili Zhao, Matthias Driess

Institutions: Technische Universität Berlin, Nanjing Tech University, State Key Laboratory of Materials-Oriented Chemical Engineering

Language: English

Topic: Synthesis and characterization of novel inorganic/organometallic compounds

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,250

Funders: Deutsche Forschungsgemeinschaft, State Key Laboratory of Chemical Resource Engineering, State Key Laboratory of Novel Software Technology, Foundation Research Project of Jiangsu Province