Kinetic Protection of a Water-Soluble Olefin Metathesis Catalyst for Potential Use under Biological Conditions

被引:5
作者
James, Catriona C. [1 ]
Laan, Petrus C. M. [1 ]
de Bruin, Bas [1 ]
Reek, Joost N. H. [1 ]
机构
[1] Univ Amsterdam, Van t Hoff Inst Mol Sci, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands
关键词
homogeneous catalysis; bioinorganic chemistry; metathesis; kinetics; RING-CLOSING METATHESIS; CONTAINING HETEROCYCLES; RUTHENIUM CATALYSTS; POLYMERIZATION; DECOMPOSITION; CHEMISTRY; BEARING; GRUBBS; COMPLEXES; MECHANISM;
D O I
10.1002/cctc.202201272
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Olefin metathesis catalysts like AquaMet are vulnerable to different decomposition pathways under biologically relevant conditions. Currently, stabilizing strategies are focused on approaches with limited relevance for application under biologically relevant conditions. Initial attempts to stabilise AquaMet by encapsulation within a supramolecular metallocage showed that the nitrate counterions of the cage improve the activity of the catalyst. We show that the chloride ligands of AquaMet can be replaced with nitrates by simple anion-exchange. Catalytic studies into metathesis of a diallyl substrate showed that the presence of nitrate generates higher yields of the ring-closed product compared to AquaMet alone, under aqueous and biological conditions. Kinetic studies support that the nitrate-containing catalyst both initiates faster and performs catalysis at a much faster rate than AquaMet, while the rate of catalyst deactivation was similar. This new strategy of kinetic protection of a transition metal catalyst may have future applications for other catalytic reactions applied in vivo.
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页数:8
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