“Alkaline-Earth Metals in a Box”: Structures of Solvent-Separated Ion Pairs

Harder, Sjoerd; Feil, Florian; Repo, Timo

doi:10.1002/1521-3765(20020503)8:9<1991::aid-chem1991>3.0.co;2-9

Cited by 58 publications

(47 citation statements)

References 7 publications

(8 reference statements)

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“…ii) we can predict the dimensionality of supramolecular compounds based on [M(L) n (H 2 O) [1][2][3][4] vi) Aryloxides allow full substitution of iodide from the initial alkaline earth metal iodide. vii) In the last three cases, new alkaline earth metal clusters could be obtained which are constructed in a similar way to transition metal clusters.…”

Section: Discussionmentioning

confidence: 99%

“…Under these conditions, the number of water molecules coordinated to the alkaline earth metal cation, directs the dimensionality of the final compound. A compound with one water molecule, like [Ba(triglyme) 2 (Fig. 4a, b, c and d, for 8, 9, 10 and 11 respectively).…”

Section: -12mentioning

confidence: 99%

“…This "structural genealogy tree" for BaI 2 could also be transferred to SrI 2 and Ba(OTf) 2 The eight oxygen atoms around Ba1 form a square antiprism. Four of the six triflate anions are l 3 -and two are l 2 -bridging ligands, whereas the THF-molecules act as terminal ligands (Fig.…”

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confidence: 94%

“…Even with excess LiOR, R = H, t Bu, we were unable to take off more than 50% of the initial iodide under the commonly used reaction conditions. When six equivalents of SrI 2 are reacted with nine equivalents of NaO t Bu in a mixture of THF and hexanes in the presence of PhN(H)Li, the monocrystalline compound [Li(thf) 4 ] + [{Sr 6 (O)(l 3 -I)(I) 2 …”

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confidence: 99%

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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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Section: Discussionmentioning

confidence: 99%

Section: -12mentioning

confidence: 99%

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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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“…These dimensions and the associated bond angles are very similar to those seen in the structure of [Mg 2 Cl 3 (THF) 6 ][C 2 P 3 ( t Bu) 2 ], which has a P-P bond length of 2.091(1) Å and P-C bond lengths of 1.731(4) to 1.748(3) Å [21]. The [Ca(THF) 6 ] 2+ dication is unexceptional, although crystallographically characterised examples of it are rare [31].…”

Section: Tablementioning

confidence: 99%

Facile preparation of trimethylsilylphosphaalkyne and its conversion to polyphospholide anions

Mansell

Green

Kilby

et al. 2010

Comptes Rendus. Chimie

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Alkaline Earth Metals: Organometallic Chemistry

Alexander

Guino-o

Zuniga

et al. 2005

Encyclopedia of Inorganic Chemistry

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The organometallic chemistry of the alkaline earth metals has undergone a renaissance during the last decade with exciting novel uses of the organomagnesium reagents in synthetic chemistry to significantly extend the utility of these well‐developed reagents. With the development of the organometallic chemistry of the heavier metals significantly lagging behind, and past work mainly focusing on and establishing π‐bonded metal–ligand systems, intense research efforts during the last decade have contributed significantly to expand the understanding of the organometallic compounds of these metals, establishing σ‐bonded organometallic compounds for the heavy alkaline earth metals. This improved insight did not only provide the basis for a more detailed understanding of the metal–ligand bonding characteristics, but also paved the way towards the successful applications of the compounds as polymerization initiators and in organic synthetic chemistry. This article summarizes some of the recent, exciting developments in regards to alkaline earth organometallics.

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“Alkaline-Earth Metals in a Box”: Structures of Solvent-Separated Ion Pairs

Cited by 58 publications

References 7 publications

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

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

Facile preparation of trimethylsilylphosphaalkyne and its conversion to polyphospholide anions

Alkaline Earth Metals: Organometallic Chemistry

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