title: Synthesis and structural comparison of a series of divalent Ln(Tp(R,R)')2 (Ln = Sm, Eu, Yb) and trivalent Sm(Tp(Me2))2X (X = F, Cl, I, BPh4) complexes.
abstract: Reaction of LnI2 (Ln = Sm, Yb) with two equivalents of NaTp(Me2) or reduction of Eu(Tp(Me2))2OTf gives good yields of the highly insoluble homoleptic Ln(II) complexes, Ln(Tp(Me2))2 (Ln = Sm (1a), Yb (2a), Eu (3a)). Use of the additionally 4-ethyl substituted Tp(Me2,4Et) ligand produces the analogous, but soluble Ln(Tp(Me2,4Et))2 (1-3b) complexes. Soluble compounds are also obtained with the Tp(Ph) and Tp(Tn) ligands (Tn = thienyl), Ln(Tp(Ph))2 (Ln = Sm, 1c; Yb, 2c) and Ln(Tp(Tn))2 (Ln = Sm, 1d; Yb, 2d). To provide benchmark parameters for structural comparison the series of Sm(Tp(Me2))2X complexes (X = F, 1e; Cl, 1f; Br, 1g; I, 1h; BPh4, 1j) were prepared either via oxidation of the Sm(Tp(Me2))2 or salt metathesis from SmX3 (X = Cl, Br, I). The solid-state structures of 1-3a, 1b, 1-2c and 1e, 1f, 1h, and 1j were determined by single-crystal X-ray diffraction. The homoleptic bis-Tp complexes are all six-coordinate with trigonal antiprismatic geometries, planes of the kappa(3)-Tp ligands are parallel to one another. In the series of Sm(Tp(Me2))2X complexes the structure changes from seven-coordinate molecular compounds, with intact Sm-X bonds, for X = F, Cl, to six-coordinate ionic structures [Sm(Tp(Me2))2]X (X = I, BPh4), suitable crystals of the bromide compound could not be obtained. The dependence of the structures on the size of X is understandable in terms of the interplay between the size of the cleft that the [Sm(Tp(Me2))2](+) fragment can make available and the donor ability of the anionic group toward the hard Sm(III) center.
authors.affiliation: Christopher Ingold Laboratories, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
authors.forename: A C
authors.initials: AC
authors.lastname: Hillier
authors.forename: X
authors.initials: X
authors.lastname: Zhang
authors.forename: G H
authors.initials: GH
authors.lastname: Maunder
authors.forename: S Y
authors.initials: SY
authors.lastname: Liu
authors.forename: T A
authors.initials: TA
authors.lastname: Eberspacher
authors.forename: M V
authors.initials: MV
authors.lastname: Metz
authors.forename: R
authors.initials: R
authors.lastname: McDonald
authors.forename: A
authors.initials: A
authors.lastname: Domingos
authors.forename: N
authors.initials: N
authors.lastname: Marques
authors.forename: V W
authors.initials: VW
authors.lastname: Day
authors.forename: A
authors.initials: A
authors.lastname: Sella
authors.forename: J
authors.initials: J
authors.lastname: Takats