Lithium Aryloxo Magnesiates:  an Examination of Ligand Size and Donor Effects

Zuniga, Maria Felisa; Kreutzer, Johannes; Teng, Weijie; Ruhlandt‐Senge, Karin

doi:10.1021/ic701423r

Cited by 26 publications

(33 citation statements)

References 36 publications

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“…, whereas heterobimetallic species could be prepared in toluene. [25] Furthermore, treatment of 3 ]. [11] Two unexpected colour variations were observed in the products.…”

Section: Resultsmentioning

confidence: 99%

“…[17] The Ba···Ba lengths in 12·PhMe, 13 and 14 (3.902(1), 3.865 (1) 4 ]·PhMe [11] and [Sr 2 A C H T U N G T R E N N U N G (Odpp) 4 ]·PhMe, [17] After adjusting for the differences in the ionic radii of the four-coordinate Ln 3 + ion, [16] the Sm À O bond lengths in the anion of 12·PhMe are in good agreement with the Yb À O bond lengths in the anion of 1·PhMe (2.053(6)-2.094 (7) ), [11] as are the YbÀO bond lengths in 13 (2.052(2)-2.071 (2) ). There are very few tetra-coordinated magnesium alkoxides or aryloxides that can be compared to the [25] and [MgA C H T U N G T R E N N U N G (OAr 3 ) 2 A C H T U N G T R E N N U N G (thf) 2 ] (OAr 3 = 2,6-di-tert-butyl-phenolate), [31] or a bidentate donor, as in [MgA C H T U N G T R E N N U N G (OAr 3 ) 2…”

Section: Structures Containing a [Ca 2 A C H T U N G T R E N N U N G mentioning

confidence: 99%

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Charge‐Separated and Molecular Heterobimetallic Rare Earth–Rare Earth and Alkaline Earth–Rare Earth Aryloxo Complexes Featuring Intramolecular Metal–π‐arene Interactions

Deacon

Junk

Moxey

et al. 2009

Chemistry A European J

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Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

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“…, whereas heterobimetallic species could be prepared in toluene. [25] Furthermore, treatment of 3 ]. [11] Two unexpected colour variations were observed in the products.…”

Section: Resultsmentioning

confidence: 99%

Section: Structures Containing a [Ca 2 A C H T U N G T R E N N U N G mentioning

confidence: 99%

Charge‐Separated and Molecular Heterobimetallic Rare Earth–Rare Earth and Alkaline Earth–Rare Earth Aryloxo Complexes Featuring Intramolecular Metal–π‐arene Interactions

Deacon

Junk

Moxey

et al. 2009

Chemistry A European J

Self Cite

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“…[13] The rate of halogen-magnesium exchange not only depends on the electronic properties and the type of halogen atoms, but also on the form of magnesium reagents. Grignard reagents (RMgX) and lithium organomagnesiates (R 3 MgLi and RMgCl·LiCl) [14] are frequently used to produce functionalized alkenyl Grignard reagents. This part will focus on the preparation of functionalized alkenylG rignard reagents from different magnesium reagents and give ab rief introduction on the application of alkenyl Grignard reagents.…”

Section: Alkenyl Grignard Reagentsmentioning

confidence: 99%

Alkenyl Magnesium Compounds: Generation and Synthetic Application

Zhu

Liu

et al. 2018

Chemistry A European J

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Alkenyl magnesium compounds have received much attention in synthetic organic chemistry because of their high reactivity. This review summarizes three types of alkenyl magnesium compounds which contain at least one [Mg-C=C] fragment, for example, (1) alkenyl Grignard reagents prepared by halogen-magnesium exchange reaction; (2) alkenyl magnesium carbenoids prepared by halogen-magnesium exchange reaction or sulfoxide-magnesium exchange reaction; (3) magnesacarbocycles containing at least one alkenyl magnesium bond prepared from Zr- or Ti-catalyzed cyclomagnesation or transmetalation, as well as their further reactions and applications.

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“…Hybrid inorganic-organic materials combining lithium and magnesium are known in a few organometallic complexes [25][26][27]. Yet, to date, extended lithium-magnesium coordination networks have not been reported.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, if the targeted material is intended to minimize the gravimetric contributions of metal centers to the overall compound, frameworks which include heavier transition and rare earth metals would be a poor approach. However, extended networks combining the lightweight s-block metals magnesium and lithium could be used to construct lightweight MOFs with new, interesting structures.Hybrid inorganic-organic materials combining lithium and magnesium are known in a few organometallic complexes [25][26][27]. Yet, to date, extended lithium-magnesium coordination networks have not been reported.…”

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confidence: 99%