Clathrochelates meet phosphorus: thiophosphorylation of Fe(II) dichloroclathrochelate precursor, synthesis of N,S-donor macrobicyclic ligands and their Pd(II) complexes as potent catalysts of Suzuki cross-coupling reaction.
Nucleophilic substitution of an iron(ii) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(ii) ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(ii) complexes, with a minor distortion caused by intramolecular interactions. The Pd(2+) ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova st., 119991 Moscow, Russian Federation. voloshin@ineos.ac.ru.
Oleg I
OI
Artyushin
Irina L
IL
Odinets
Ekaterina V
EV
Matveeva
Anna V
AV
Vologzhanina
Oleg A
OA
Varzatskii
Sergey E
SE
Lyubimov
Yan Z
YZ
Voloshin