Lanthanide and uranium complexes with an SPS-based pincer ligand

Thérèse Arliguie; Marjolaine Doux; Nicolas Mézailles; Pierre Thuéry; Pascal Le Floch; Michel Ephritikhine

doi:10.1021/ic061364g

Lanthanide and uranium complexes with an SPS-based pincer ligand

Inorg Chem. 2006 Nov 27;45(24):9907-13. doi: 10.1021/ic061364g.

Authors

Thérèse Arliguie¹, Marjolaine Doux, Nicolas Mézailles, Pierre Thuéry, Pascal Le Floch, Michel Ephritikhine

Affiliation

¹ Service de Chimie Moléculaire, DSM, DRECAM, CNRS URA 331, CEA/Saclay, 91191 Gif-sur-Yvette, France. therese.arliguie@cea.fr

PMID: 17112289
DOI: 10.1021/ic061364g

Abstract

Reactions of Ln(BH4)3(THF)n and [Li(Et2O)]SPS(Me)], the lithium salt of an anionic SPS pincer ligand composed of a central hypervalent lambda4-phosphinine ring bearing two ortho-positioned diphenylphosphine sulfide sidearms, led to the monosubstituted compounds [Ln(BH4)2(SPS(Me))(THF)2] [Ln = Ce (1), Nd (2)], while the homoleptic complexes [Ln(SPS(Me))3] [Ln = Ce (3), Nd (4)] were obtained by treatment of LnX3 (X = I, BH4) with [K(Et2O)][SPS(Me)]. The [UX2(SPS(Me))2] complexes [X = Cl (5), BH4 (6)] were isolated from reactions of UX4 and the lithium or potassium salt of the [SPS(Me)]- anion. The X-ray crystal structures of 1.1.5THF, 2.1.5THF, 3.2THF.2Et2O, and 5.4py reveal that the flexible tridentate [SPS(Me)]- anion is bound to the metal as a tertiary phosphine with electronic delocalization within the unsaturated parts of the ligand.