Substitution Reactions on CaI<sub>2</sub>: Synthesis of Mixed Metal Lithium‐Calcium‐Phenolates, and Cluster Transformation as a Function of Solvent

Maudez, William; Häußinger, Daniel; Fromm, Katharina M.

doi:10.1002/zaac.200600170

Cited by 28 publications

(23 citation statements)

References 69 publications

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“…22,23,37,40 This straightforward access to mixed metal aryl-and alkoxides inspired us to use this approach, replacing alkaline earth metal halides by chromium dihalides as starting compounds due to their better solubility and in spite of the sensitivity of such compounds to humidity. 45 Very similar to a compound described by us, [Ca(OPh) 8 Li 6 -(THF) 6 ], 42 the literature reports on a Cr(II) compound, namely, [Cr(OPh) 5 Li 3 (THF) 3 ] 2 , A (Figure 1), described by Edema et al 46 We were intrigued by this structure, expecting it to be easily oxidized yielding new Cr(III) species which are otherwise not available by direct synthesis from Cr(III) salts and reactions with phenolates. Indeed, the known species of Cr(III) clusters and aryloxide ligands are based on substituted phenolates, 46,48−53 while unsubstituted Cr(III) phenolates are unknown to the best of our knowledge.…”

Section: ■ Introductionsupporting

confidence: 70%

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Crochet

Brog

Fromm

2015

Crystal Growth & Design

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Oxidative substitution reactions of chromium(II) chloride with lithium phenoxide in the presence of water give access to new polynuclear chromium(III) aryloxide complexes and coordination polymers. While a one-dimensional coordination polymer based on chromium(III), [Cr 2 (μ 3 -OPh) 2 (μ-OPh) 6 (μ-OH)(μ 3 -Li) 4 (μ 3 -Cl) 2 Li(THF) 6 ] n , is first obtained by serendipity, the controlled addition of water to the initial Cr(II) complex as well as variation of the stoichiometry lead to three new discrete chromium(III) aggregates, namely, [Cr(OPh) The properties of such polymetallic compounds depend on (a) the types and proportions of metallic species, and (b) the use of ligands allowing the tuning of the properties. Indeed, depending of the ligand, we obtained a different configuration of complex which in the case of the bridging ligand, changes angles and distances between metals ions. The bulkiness of the ligand has a major role in the case where accessibility of metal center is necessary, e.g., in catalysis. 5,6 In our group, we have investigated alkali and alkaline earth metal compounds in order to study their behavior in nonaqueous solvents, their analogy to transition metals, and possible applications in oxide materials. 2,22−43 We have previously shown that group 2 metal halides may act as starting materials for both homometallic alkaline earth and mixed-metal alkali and alkaline earth aryl and alkoxide cage compounds obtained from (partial) abstraction of halide. 2,38,39,42−44 Depending on the bulk of the R group on the alkoxide or aryloxide reagent and the nature of the alkali metal and the solvent of crystallization, different structures were achieved. 36,37,43,44 In this context, we have also used calixarenes, which can be understood as cyclic polyphenols, to obtain lithium polyaryloxides. 22,23,37,40 This straightforward access to mixed metal aryl-and alkoxides inspired us to use this approach, replacing alkaline earth metal halides by chromium dihalides as starting compounds due to their better solubility and in spite of the sensitivity of such compounds to humidity. 45Very similar to a compound described by us, [Ca(OPh) 8 Li 6 -(THF) 6 ], 42 the literature reports on a Cr(II) compound,

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Section: ■ Introductionsupporting

confidence: 70%

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Crochet

Brog

Fromm

2015

Crystal Growth & Design

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“…26 turns out to be sensitive to traces of air and humidity, and reacts easily with DME to yield [Ca 2 (dme) 2 (lOPh) 6 {Li(dme)} 2 ], 27. 28 This cluster consists of a bent chain arrangement of Li-Ca-Ca-Li in which the metal ions are pairwise bridged by two phenolate groups each (Fig. 12).…”

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Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents

Fromm

2006

Dalton Trans.

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This overview on one of the subjects treated in our group deals with the synthesis and study of low-dimensional polymer and molecular solid state structures formed with alkaline earth metal ions in non-aqueous solvents. We have chosen several synthetic approaches in order to obtain such compounds. The first concept deals with the "cutting out" of structural fragments from a solid state structure of a binary compound, which will be explained with reference to BaI 2 . Depending on the size and concentration of oxygen donor ligands, used as chemical scissors on BaI 2 , three-, two-, one-and zero-dimensional derived adducts of BaI 2 are obtained, comparable to a structural genealogy tree for BaI 2 . A second part deals with the supramolecular approach for the synthesis of low dimensional polymeric compounds based on alkaline earth metal iodides, obtained by the combination of metal ion coordination with hydrogen bonding between the cationic complexes and their anions. Certain circumstances allow rules to be established for the prediction of the dimensionality of a given compound, contributing to the fundamental problem of structure prediction in crystal engineering. A third section describes a synthetic approach for generating pure alkaline earth metal cage compounds as well as alkali and alkaline earth mixed metal clusters. A first step deals with different molecular solvated alkaline earth metal iodides which are investigated as a function of the ligand size in non-aqueous solvents. These are then reacted with some alkali metal compound in order to partially or totally eliminate alkali iodide and to form the targeted clusters. These unique structures of ligand stabilized metal halide, hydroxide and/or alkoxide and aryloxide aggregates are of interest as potential precursors for oxide materials and as catalysts. Approaches to two synthetic methods of the latter, sol-gel and ( Elsevier, Amsterdam, 2004, vol. 3, 1-92). Finally, the physical properties of some of our compounds are described qualitatively in order to show the wide spectrum of possibilities and potential applications for chemistry in this field.

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“…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.…”

Section: S-block Compoundsmentioning

confidence: 99%

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

Gschwind¹,

Crochet²,

Maudez³

et al. 2010

Chimia

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Heterometallic oxides are used as materials in many applications, e.g. from ferroelectrics to superconductors. Making these compounds usually requires high temperatures and long reaction times. Molecular precursors may contribute to render their processing shorter and accessible at lower temperatures, thus cheaper in energy and time. In this review article, different approaches toward oxide materials will be shown, starting with homometallic clusters and coordination polymers and highlighting recent results with heterometallic single source precursors. On the way to the latter, we came across many exciting results which themselves allowed applications in different fields. This work will give an overview on how these fields were brought together for the current mixed metallic compounds as precursors for heterometallic oxides.

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Substitution Reactions on CaI₂: Synthesis of Mixed Metal Lithium‐Calcium‐Phenolates, and Cluster Transformation as a Function of Solvent

Cited by 28 publications

References 69 publications

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents

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

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Substitution Reactions on CaI2: Synthesis of Mixed Metal Lithium‐Calcium‐Phenolates, and Cluster Transformation as a Function of Solvent

Cited by 28 publications

References 69 publications

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents

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

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Substitution Reactions on CaI₂: Synthesis of Mixed Metal Lithium‐Calcium‐Phenolates, and Cluster Transformation as a Function of Solvent