Regioisomerism in coordination chemistry: oxidative addition of a bifunctional ligand to palladium, stabilized with 1,2-bis(diphenylphosphino)ethane

K A Martyanov; V K Cherkasov; G A Abakumov; E V Baranov; A S Shavyrin; V A Kuropatov

doi:10.1039/c7dt03891g

Regioisomerism in coordination chemistry: oxidative addition of a bifunctional ligand to palladium, stabilized with 1,2-bis(diphenylphosphino)ethane

Dalton Trans. 2017 Dec 12;46(48):16783-16786. doi: 10.1039/c7dt03891g.

Authors

K A Martyanov¹, V K Cherkasov¹, G A Abakumov¹, E V Baranov¹, A S Shavyrin¹, V A Kuropatov¹

Affiliation

¹ G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, GSP-445, Tropinina str. 49, Nizhny Novgorod, Russia. konmart@iomc.ras.ru viach@iomc.ras.ru.

PMID: 29165468
DOI: 10.1039/c7dt03891g

Abstract

A unique phenomenon of regioisomerism in coordination chemistry was discovered: the reaction of a sterically hindered o-quinone annelated with a dithiete ring with Pd₂dba₃ in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a mixture of two regioisomers: catecholate 3Cat and dithiolate 3Dit. Both isomers were isolated in crystalline form and characterized by NMR, IR and X-ray diffractometry studies. DFT calculations reveal that the 3Dit species is more thermodynamically stable than the isomer 3Cat. Isomerization of 3Cat to 3Dit in solution was observed.