Catalytic activation of remote alkenes through silyl-rhodium(III) complexes

被引:10
作者
Prieto-Pascual, Unai [1 ]
de Morentin, Aitor Martinez [1 ]
Choquesillo-Lazarte, Duane [2 ]
Rodriguez-Dieguez, Antonio [3 ]
Freixa, Zoraida [1 ,4 ]
Huertos, Miguel A. [1 ,4 ]
机构
[1] Univ Pais Vasco UPV EHU, Fac Quim, San Sebastian 20018, Spain
[2] UGR, Lab Estudios Cristalog, IACT, CSIC, Granada 18071, Spain
[3] Univ Granada, Dept Quim Inorgan, Granada 18071, Spain
[4] Basque Fdn Sci, IKERBASQUE, Bilbao 48011, Spain
关键词
IRON CATALYSTS; HOMOGENEOUS CATALYSIS; HYDROSILYLATION; HYDROSILATION; MECHANISM; STRATEGY; RHODIUM; ALKYL; BOND;
D O I
10.1039/d3dt00624g
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The tandem isomerization-hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(III) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate ligands, 8-(dimethylsilyl)quinoline (L1), 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3), have been used to synthesize three neutral [RhCl(H)(L)PPh3] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L)(PPh3)(2)][BAr4F] (2-L1, 2-L2 and 2-L3) Rh(iii) complexes. Among the neutral compounds, 1-L2 could be characterized in the solid state by X-ray diffraction showing a distorted trigonal bipyramidal structure. Neutral complexes (1-L1, 1-L2 and 1-L3) failed to catalyze the hydrosilylation of olefins. On the other hand, the cationic compound 2-L2 was also characterized by X-ray diffraction showing a square pyramidal structure. The unsaturated and cationic Rh(iii) complexes 2-L1, 2-L2 and 2-L3 showed significant catalytic activity in the hydrosilylation of remote alkenes, with the most sterically hindered (2-L2) being the most active one.
引用
收藏
页码:9090 / 9096
页数:7
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