Related Experiment Video
Updated: Jul 4, 2026
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
DFT study on isomerization and decomposition of cuprous dialkyldithiophosphate and its reaction with alkylperoxy
Yi Luo1, Satoshi Maeda, Koichi Ohno
1Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan.
Abstract:
The cuprous dialkyldithiophosphate [(RO)2PS2Cu, CuDDP] as an antioxidant has been industrially used in lubricating oil. In this paper, for the first time, a computational study has been carried out for CuDDP. The scaled hypersphere search method has been used to explore the isomerization and decomposition pathways of (HO)2PS2Cu, a model compound of CuDDP, and its reaction with CH3OO* radical. The calculations were performed at the B3LYP level of theory. The results show that the most stable structure of (HO)2PS2Cu has pseudo-C2v symmetry and a four-membered ring constructed by P, Cu, and two S atoms. The bond-rearrangement isomerization leading to a (H)O-bridging structure is kinetically feasible. Three dissociation channels have been found for (HO)2PS2Cu, which require high energy (>60 kcal/mol) under the investigated condition. The reaction of (HO)2PS2Cu with CH3OO* includes bond-rearrangement isomerization and the decomposition of CH3OO* moiety. The (HO)2PS2Cu-assisted CH3OO* decomposition occurs via its O-O bond cleavage or the C-O bond dissociation. The former decomposition manner has been computed to be preferable over the latter at low temperature, but calculations suggested for the latter decomposition manner at higher temperature. Such a decomposition reaction, which is endothermic but possible, may be related to the antioxidation process of CuDDP.
More Related Videos
Related Concept Videos
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Radical Formation: Elimination
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Regioselectivity of Electrophilic Additions-Peroxide Effect

