Issue 25, 2014

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§

Abstract

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 Pd2+ ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.

Graphical abstract: 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

Supplementary files

Article information

Article type
Paper
Submitted
20 Dec 2013
Accepted
28 Mar 2014
First published
01 Apr 2014

Dalton Trans., 2014,43, 9677-9689

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

O. I. Artyushin, I. L. Odinets, E. V. Matveeva, A. V. Vologzhanina, O. A. Varzatskii, S. E. Lyubimov and Y. Z. Voloshin, Dalton Trans., 2014, 43, 9677 DOI: 10.1039/C3DT53590H

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