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Updated: Jun 12, 2025
Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Dinitrogen silylation catalyzed by silylene cobalt(I) and silylene iron(I) chlorides
Qingqing Fan1, Qingshuang Li1, Hongjian Sun1
1School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250100 Jinan, People's Republic of China. xli63@sdu.edu.cn.
Abstract:
In this contribution, Co(PMe3)3Cl (1), bis(silylene) cobalt chlorides Co(LSi:)2(PMe3)2Cl (LSi: = {PhC(NBu)2}SiCl (2); {p-CH3C6H4C(NBu)2}SiCl (3); and {p-BuC6H4C(NBu)2}SiCl (4)) and bis(silylene) iron chlorides Fe(LSi:)2(PMe3)2Cl (LSi: = {PhC(NBu)2}SiCl (5); {p-CH3C6H4C(NBu)2}SiCl (6); {p-BuC6H4C(NBu)2}SiCl (7) and Fe(PMe3)2Cl2 (8)) were synthesized to study the effects of different metals and silylene ligands on the catalytic activity of complexes 1-8 in dinitrogen silylation reaction. The experimental results indicate that there is no substantial difference in catalytic activity between the phosphine cobalt complex 1 and the silylene cobalt chlorides 2-4 although the cobalt silylene complex 2 has slightly better catalytic activity than complexes 1, 3 and 4 in the dinitrogen silylation. Silylene iron complexes 5-7 are more active than the phosphine iron complex 8. Among the three silylene iron(I) chlorides 5-7, complex 5 is the most effective catalyst for dinitrogen silylation and 402 equiv. of N(SiMe3)3 could be obtained per Fe atom. In the dinitrogen silylation reaction catalyzed by iron complexes, the introduction of the silylene ligand made the silylene iron complexes 5-7 more active than the phosphine iron complex 8. In addition, iron chlorides 5-8 are more effective catalysts than cobalt(I) chlorides 1-4 for the dinitrogen silylation reaction. Complexes 3, 4, 6 and 7 were new complexes, and their molecular structures were determined by single crystal X-ray diffraction analysis.
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