Coordinating ability of anions and solvents towards transition metals and lanthanides

Abstract

A scale that attempts to quantify the weakly coordinating character of a variety of solvents and anions is presented. For each group (solvent or anion), a coordinating ability index has been calculated, based on the probability of it being coordinated in the presence of a transition metal atom, compared to the probability of finding it as a solvation molecule or as non-coordinating counterion in a crystal structure. The corresponding index is also defined for the same groups in the presence of lanthanides, and the similarities and differences are discussed.

Tuning the Structure and Properties of Lanthanoid Coordination Polymers with an Asymmetric Anilato Ligand

“…As expected, given the great ability of these solvents to coordinate Ln(III) ions [41], the solvents appear coordinated to the Ln(III) ion in the final compounds. The slow diffusion of the reagents allowed the synthesis of good quality single crystals for the determination of the X-ray structure in all cases.…”

“…Given these above-mentioned results: (i) the luminescence of the nitranilato derivative with Ho(III) [37], (ii) the intrinsic luminescence of the chlorocyananilato ligand [39,40], (iii) the luminescence shown by many Ln(III) ions, (iv) the above-mentioned ability of anilato ligands to form 2D lattices with all the Ln(III) ions [31,33,36] (Tables 1-3), and (v) the capacity shown by some coordinating solvents to modify these 2D lattices [35,36], we have initiated a detailed study to prepare and characterize the complete series of compounds with Ln(III) ions and the ligand chlorocyananilato. Furthermore, we have decided to use different solvents as H 2 O, DMF, and DMSO, since these solvents have a high ability to coordinate to the Ln(III) ions [41], and are therefore expected to modulate not only the luminescent properties, but also the structure of the resulting compounds, as has been very recently demonstrated by some of us [36] …”

Fluorocarbons Modulate the Coordination Sphere of f‐Element Complexes

“…[3] Nevertheless, coordination of fluorocarbons to metal centers, R À F!M, is a highly desirable goal since it might result in weakening of the strong CÀF bond and thus favor its activation [4] Fluorocarbon coordination is favored for highly electrophilic metal centers, especially if the R À F unit is anchored to the metal through another donor end (Scheme 1 a). [5] Ligands of diverse complexity containing fluorinated aryl groups are particularly suited for that purpose.…”

Synthesis, Structures and Properties of Cobalt Thiocyanate Coordination Compounds with 4-(hydroxymethyl)pyridine as Co-ligand

“…The synthesis of new coordination polymers with desired physical properties is a major field in coordination chemistry [1][2][3][4]. For this purpose, structure-property relationships are investigated systematically and strategies for a rational construction of their crystal structures are required.…”