Analogy of the Coordination Chemistry of Alkaline Earth Metal and Lanthanide Ln²⁺ Ions: The Isostructural Zoo of Mixed Metal Cages [IM(OtBu)₄{Li(thf)}₄(OH)] (M=Ca, Sr, Ba, Eu), [MM′₆(OPh)₈(thf)₆] (M=Ca, Sr, Ba, Sm, Eu, M′=Li, Na), and their Derivatives with 1,2‐Dimethoxyethane

Abstract

As previously shown, alkali and alkaline earth metal iodides in nonaqueous, aprotic solvents behave like transition metal halides, forming cis- and trans-dihalides with various neutral O-donor ligands. These compounds can be used as precursors for the synthesis of new mixed alkali/alkaline earth metal aggregates. We show here that Ln2+ ions form isostructural cluster compounds. Thus, with LiOtBu, 50% of the initial iodide can be replaced in MI2, M=Ca, Sr, Ba, Eu, to generate the mixed-metal alkoxide aggregates [IM(OtBu)4{Li(thf)}4(OH)], for which the M--OH contacts were investigated by theoretical methods. With M'OPh (M'=Li, Na), a new mixed-metal aryloxide cluster type [MM'6(OPh)8(thf)6] is obtained for M=Ca, Sr, Ba, Sm, Eu. Their stability versus DME (DME=1,2-dimethoxyethane) as bidentate ligand is studied.

Polymorph of Dibenzo‐24‐Crown‐8 and its Mercury Complex

“…We use non-cyclic and cyclic polyethereal ligands in order to synthesize and characterize new metal halide compounds, which can be used as precursors for oxide materials. [24][25][26][27] In this context, as well as for comparison with the literature mercury compounds mentioned above, and also comparing the conformation of the ligand upon coordination with its free form, we tested 1 as ligand for HgI 2 . Indeed, the ligand 1 as well as the starting compound HgI 2 has two polymorphic forms, the red and the yellow HgI 2 in the latter case.…”

Polyether Adducts of d‐Block Metal Compounds as Starting Materials for New Cluster Compounds

“…For CdI 2 , Hines has obtained a molecular CdI 2 with one triglyme [77]. Bridging properties of glyme were also described for alkaline earth metal cluster compounds [42], but is a very rare phenomenon. This is very likely due to energetic reasons.…”

From Alkaline Earth Ion Aggregates via Transition Metal Coordination Polymer Networks towards Heterometallic Single Source Precursors for Oxidic Materials

“…This has first led us to the field of alkali [9][10][11][12] and alkaline earth metal compounds, [13,14] of which a number of new clusters were observed. [15][16][17][18][19][20][21][22][23] Being hard metal ions, mainly O-donor ligands were chosen for the coordination to these group 1 and 2 ions. Among these ligands are charged monodentate ligands OR, R = H, alkyl, aryl, [22,23] as well as the neutral polyether ligands such as oligo dimethyl ethers, [24][25][26][27][28][29][30][31][32] crown ethers [33,34] or calixarene ligands.…”