Murphy, Damien Martin ![]() ![]() ![]() ![]() |
Abstract
The mode of chiral interaction between a series of asymmetric epoxides (propylene oxide, butylene oxide, epifluorohydrin and epichlorohydrin) and a chiral vanadyl salen complex, N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino-vanadium (IV) oxide, [VO(1)], was investigated by a range of electron magnetic resonance techniques (EPR, ENDOR, HYSCORE) and DFT. Enantiomer discrimination of the weakly bound epoxides by the vanadyl complex was evident by cw-ENDOR. The origin of this discrimination was attributed to a number of factors including H-bonds, steric properties and electrostatic contributions, which collectively control the outcome of the chiral interaction. DFT revealed the role of a key H-bond, formed between the epoxide oxygen atom (Oepoxide) and the methine proton (Hexo) attached to the asymmetric carbon atom of the chiral vanadyl salen complex, thereby providing a direct pathway for stereochemical communication between complex and substrate. These findings reveal the potential importance of weak outer sphere interactions in stereoselectivities of enantioselective homogeneous catalysis.
Item Type: | Article |
---|---|
Date Type: | Publication |
Status: | Published |
Schools: | Advanced Research Computing @ Cardiff (ARCCA) Chemistry Cardiff Catalysis Institute (CCI) |
Subjects: | Q Science > QD Chemistry |
Publisher: | Royal Society of Chemistry |
ISSN: | 1463-9076 |
Last Modified: | 02 Nov 2024 17:48 |
URI: | https://orca.cardiff.ac.uk/id/eprint/6075 |
Citation Data
Cited 11 times in Scopus. View in Scopus. Powered By Scopus® Data
Actions (repository staff only)
![]() |
Edit Item |