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 thi...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 43; no. 25; pp. 9677 - 9689
Main Authors Artyushin, Oleg I, Odinets, Irina L, Matveeva, Ekaterina V, Vologzhanina, Anna V, Varzatskii, Oleg A, Lyubimov, Sergey E, Voloshin, Yan Z
Format Journal Article
LanguageEnglish
Published England 07.07.2014
Subjects
Cage
Catalysis
Catalysts
Diamines
Distortion
Ligands
Precursors
Sulfides
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Summary: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.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c3dt53590h