Diene Dissolution of the Heavier Alkaline Earth Metals

Michel, Olaf; Kaneko, Hiroshi; Tsurugi, Hayato; Yamamoto, Kōji; Törnroos, Karl W.; Anwander, Reiner; Mashima, Kazushi

doi:10.1002/ejic.201101342

Cited by 18 publications

(13 citation statements)

References 38 publications

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“…This complex proved able to transfer the ligands from barium to a holmium precursor and generate a new Ho‐based radical‐anion complex in clean fashion. In a related study, the heavily substituted 2,3‐dimethyl‐1,4‐bis(2,4‐dimethylphenyl)‐1,3‐butadiene reacted with elemental barium and catalytic iodine in thf to afford purple crystals of the diamagnetic monomer [Ba{2,3‐dimethyl‐1,4‐bis(2,4‐dimethylphenyl)‐2‐butenediide} · (thf) 4 ].…”

Section: Heteroleptic Complexesmentioning

confidence: 99%

Contemporary Molecular Barium Chemistry

Chapple

Sarazin

2020

Eur J Inorg Chem

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Driven by the many potential applications as molecular catalyst for a range of metal‐promoted transformations, the quest for well‐defined, soluble and reactive complexes of barium has attracted substantial interest in the past decade. While it has long been overlooked, barium is now one of the hotly debated metals in main group chemistry. The present review surveys the main achievements of the last 10 years in the molecular chemistry of barium, presenting along the way the key synthetic strategies that have been implemented successfully to address the specificities of barium chemistry. This includes ligand design and non‐covalent interactions. The performances of barium complexes as homogeneous catalysts for the most prominent reactions mediated by alkaline‐earth metals (hydroelementations and heterodehydrocouplings) are reviewed in conjunction with those obtained with somewhat more common calcium or strontium catalysts.

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Section: Heteroleptic Complexesmentioning

confidence: 99%

Contemporary Molecular Barium Chemistry

Chapple

Sarazin

2020

Eur J Inorg Chem

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“…This is consistent with the bonding descriptionf or the experimental Mg-diene, [40] but different from that for the previously known tetrahapto h 4 -coordination compounds such as Mg(THF) 3 (s-cis-PhCH=CHÀCH=CHPh) and M(2,3-dimethyl-1,4-diphenyl-1,3-butadiene)(THF) 4 (M = Ca and Sr). [33][34][35] In the latterc ompounds, all four carbon atoms in the butadiene ligand connect the metal atoms (Mg, Ca, Sr,a nd Ba) with p-electron donation, and the bond lengthsC 1 ÀC2 (and C3ÀC4) in these butadiene ligandsa re greater than C2ÀC3, that is, CÀC=CÀC, indicating electron transfer within the butadiene ligands.…”

Section: Nbo Analysis and Molecular Orbitalsmentioning

confidence: 99%

“…[32] Attempts have been madet os tudy the direct reactions of variousa lkaline earthm etals (Mg, Ca, Sr, and Ba) with 1,3-butadiene derivatives. [33][34][35][36] However the reported products were the complexes with p electrons donated from the hydrocarbon ligand to the exocyclic metal atoms (Mg, Ca, Sr,a nd Ba). That is, those compounds do not fall in the category of metallacycles discussed above.…”

Section: Introductionmentioning

confidence: 99%

“…For the main‐group metal elements, with small electronegativity values, it is more challenging to synthesize analogous cyclic compounds, although Grignard reagents, containing the alkaline‐earth metal magnesium, have of course been used for over one hundred years . Attempts have been made to study the direct reactions of various alkaline earth metals (Mg, Ca, Sr, and Ba) with 1,3‐butadiene derivatives . However the reported products were the complexes with π electrons donated from the hydrocarbon ligand to the exocyclic metal atoms (Mg, Ca, Sr, and Ba).…”

Section: Introductionmentioning

confidence: 99%

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The Recently Synthesized Dimagnesiabutadiene and the Analogous Dimetalla‐Beryllium, ‐Calcium, ‐Strontium, and ‐Barium Compounds

Feng

Xie

et al. 2016

Chemistry A European J

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The 2014 synthesis of the remarkable dimagnesium compound Mg [C (CH ) (Si(CH ) ) ](C H ) (C H O) may point the way to a new chapter in alkaline earth organometallic chemistry. Accordingly, we have studied the known Mg compound and the analogous Be, Ca, Sr, and Ba structures. Although most of our theoretical predictions come from density functional methods, the latter have been benchmarked using coupled cluster theory including single, double, and perturbative triplet excitations, CCSD(T) using cc-pVTZ basis sets. Among our most important predictions are the energies for dissociation to the butadiene plus the RM-MR [R=(C H ) (C H O) ; M=Be, Mg, Ca, Si, and Ba] entities. The most reliable predictions for the dissociation energies are 99-104 (Be), 85-93 (Mg), 90-99 (Ca), 83-92 (Sr), and 83-94 (Ba) kcal mol . Thus, there is reason to anticipate that the four unknown compounds should be achievable synthetically. The predicted metal-metal distances (not single bonds) are 2.89 Å (Mg⋅⋅⋅Mg), 3.46 Å (Ca⋅⋅⋅Ca), 3.75 Å (Sr⋅⋅⋅Sr), and 4.04 Å (Ba⋅⋅⋅Ba). The separated RM-MR compounds have longer M-M distances but genuine metal-metal single bonds. This perhaps counter intuitive result is due to the presence of the bridging carbons in the alkaline earth butadiene compounds. All five compounds incorporate metal-carbon ionic interactions.

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“…For example, metallacyclopentadienes of the alkaline-earth metals (group 2 elements in the Periodic Table) have not been reported, although alkaline-earth metallacyclopentenes M K (RCHRC=CRC L HR) are known and magnesiacyclopentadienes are proposed in some reactions as elusive intermediates. [2,3] Organomagnesium compounds (Grignard reagents or diorganomagnesium reagents) are among the most useful organometallic reagents for synthetic chemistry and related science. [4, 5b] Magnesiacyclopentadienes are expected to have unique molecular structures and be useful, but display different reaction chemistry from normal Grignard reagents.…”

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confidence: 99%

Magnesiacyclopentadienes as Alkaline‐Earth Metallacyclopentadienes: Facile Synthesis, Structural Characterization, and Synthetic Application

Wei,

Liu,

Zhan

et al. 2014

Angewandte Chemie

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Metallacyclopentadienes have attracted much attention as building blocks for synthetic chemistry as well as key intermediates in many metal-mediated or metal-catalyzed reactions. However, metallacyclopentadienes of the alkalineearth metals have not been reported, to say nothing of their structures, reaction chemistry, and synthetic applications. In this work, the first series of magnesiacyclopentadienes, spirodilithio magnesiacyclopentadienes, and dimagnesiabutadiene were synthesized from 1,4-dilithio 1,3-butadienes. Singlecrystal X-ray structural analysis of these magnesiacycles revealed unique structural characteristics and bonding modes. Their reaction chemistry and synthetic application were preliminarily studied and efficient access to amino cyclopentadienes was established through their reaction with thioformamides. Experimental and DFT calculations demonstrated that these magnesiacyclopentadienes could be regarded as bis(Grignard) reagents wherein the two MgÀC(sp 2 ) bonds have a synergetic effect when reacting with substrates.

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Diene Dissolution of the Heavier Alkaline Earth Metals

Cited by 18 publications

References 38 publications

Contemporary Molecular Barium Chemistry

Contemporary Molecular Barium Chemistry

The Recently Synthesized Dimagnesiabutadiene and the Analogous Dimetalla‐Beryllium, ‐Calcium, ‐Strontium, and ‐Barium Compounds

Magnesiacyclopentadienes as Alkaline‐Earth Metallacyclopentadienes: Facile Synthesis, Structural Characterization, and Synthetic Application

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