Journal ArticleDOI
β-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies
Simon J. Bonyhady,Cameron Jones,Sharanappa Nembenna,Andreas Stasch,Alison J. Edwards,Garry J. McIntyre +5 more
TLDR
The preparation and characterization of a series of magnesium(II) iodide complexes incorporating beta-diketiminate ligands of varying steric bulk and denticity, namely, [(ArNCMe)(2)CH](-) (Ar=phenyl), mesityl ((Mes)Nacnac), or 2,6-diisopropylphenyl (Dipp, ( Dipp)NACnac) are reported.Abstract:
The preparation and characterization of a series of magnesium(II) iodide complexes incorporating beta-diketiminate ligands of varying steric bulk and denticity, namely, [(ArNCMe)(2)CH](-) (Ar=phenyl, ((Ph)Nacnac), mesityl ((Mes)Nacnac), or 2,6-diisopropylphenyl (Dipp, (Dipp)Nacnac)), [(DippNCtBu)(2)CH](-) ((tBu)Nacnac), and [(DippNCMe)(Me(2)NCH(2)CH(2)NCMe)CH](-) ((Dmeda)Nacnac) are reported The complexes [((Ph)Nacnac)MgI(OEt(2))], [((Mes)Nacnac)MgI(OEt(2))], [((Dmeda)Nacnac)MgI(OEt(2))], [((Mes)Nacnac)MgI(thf)], [((Dipp)Nacnac)MgI(thf)], [((tBu)Nacnac)MgI], and [((tBu)Nacnac)MgI(DMAP)] (DMAP=4-dimethylaminopyridine) were shown to be monomeric by X-ray crystallography In addition, the related beta-diketiminato beryllium and calcium iodide complexes, [((Mes)Nacnac)BeI] and [{((Dipp)Nacnac)CaI(OEt(2))}(2)] were prepared and crystallographically characterized The reductions of all metal(II) iodide complexes by using various reagents were attempted In two cases these reactions led to the magnesium(I) dimers, [((Mes)Nacnac)MgMg((Mes)Nacnac)] and [((tBu)Nacnac)MgMg((tBu)Nacnac)] The reduction of a 1:1 mixture of [((Dipp)Nacnac)MgI(OEt(2))] and [((Mes)Nacnac)MgI(OEt(2))] with potassium gave a low yield of the crystallographically characterized complex [((Dipp)Nacnac)Mg(mu-H)(mu-I)Mg((Mes)Nacnac)] All attempts to form beryllium(I) or calcium(I) dimers by reductions of [((Mes)Nacnac)BeI], [{((Dipp)Nacnac)CaI(OEt(2))}(2)], or [{((tBu)Nacnac)CaI(thf)}(2)] have so far been unsuccessful The further reactivity of the magnesium(I) complexes [((Mes)Nacnac)MgMg((Mes)Nacnac)] and [((tBu)Nacnac)MgMg((tBu)Nacnac)] towards a variety of Lewis bases and unsaturated organic substrates was explored These studies led to the complexes [((Mes)Nacnac)Mg(L)Mg(L)((Mes)Nacnac)] (L=THF or DMAP), [((Mes)Nacnac)Mg(mu-AdN(6)Ad)Mg((Mes)Nacnac)] (Ad=1-adamantyl), [((tBu)Nacnac)Mg(mu-AdN(6)Ad)Mg((tBu)Nacnac)], and [((Mes)Nacnac)Mg(mu-tBu(2)N(2)C(2)O(2))Mg((Mes)Nacnac)] and revealed that, in general, the reactivity of the magnesium(I) dimers is inversely proportional to their steric bulk The preparation and characterization of [((tBu)Nacnac)Mg(mu-H)(2)Mg((tBu)Nacnac)] has shown the compound to have different structural and physical properties to [((tBu)Nacnac)MgMg((tBu)Nacnac)] Treatment of the former with DMAP has given [((tBu)Nacnac)Mg(H)(DMAP)], the X-ray crystal structure of which disclosed it to be the first structurally authenticated terminal magnesium hydride complex Although attempts to prepare [((Mes)Nacnac)Mg(mu-H)(2)Mg((Mes)Nacnac)] were not successful, a neutron diffraction study of the corresponding magnesium(I) complex, [((Mes)Nacnac)MgMg((Mes)Nacnac)] confirmed that the compound is devoid of hydride ligandsread more
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Oxidative Addition and Reductive Elimination at Main-Group Element Centers
Terry Chu,Georgii I. Nikonov +1 more
TL;DR: This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements.
Journal ArticleDOI
Alkaline earths as main group reagents in molecular catalysis.
TL;DR: This review focusses on the developing state of the art in both multiple bond heterofunctionalisation and cross coupling catalysis in alkene and alkyne hydroamination and hydrophosphination catalysis and related extensions of this reactivity that allow the synthesis of a wide variety of acyclic and heterocyclic small molecules.
Journal ArticleDOI
The Road Travelled: After Main‐Group Elements as Transition Metals
TL;DR: In this article, an overview of the last 10 years since Power's seminal review, and the progress made for catalytic application is presented, where the use of low oxidation state and/or low coordinate group 13 and 14 complexes towards small molecule activation (oxidative addition step in a redox based cycle) is examined.
Journal ArticleDOI
N-heterocyclic carbene-main-group chemistry: a rapidly evolving field.
TL;DR: This Award Article targets the evolving, yet surprisingly fruitful, chemistry of N-heterocyclic carbenes with low-oxidation-state main-group elements with a valuable historical perspective.
Journal ArticleDOI
Synthesis, structure and reaction chemistry of a nucleophilic aluminyl anion
TL;DR: An anionic aluminium(i) nucleophile is synthesized in which the aluminium is formally anionic; reactions with various substrates suggest that this compound acts as the nucleophilic partner in both metal–carbon and metal–metal bond-forming reactions.
References
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Covalent radii revisited
Beatriz Cordero,Verónica Gómez,Ana E. Platero-Prats,Marc Revés,Jorge Echeverría,Eduard Cremades,Flavia Barragán,Santiago Alvarez +7 more
TL;DR: A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96 and shows a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking.
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CRYSTALS version 12: software for guided crystal structure analysis
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Sequencing Reactions with Samarium(II) Iodide.
Journal ArticleDOI
Stable Magnesium(I) Compounds with Mg-Mg Bonds
TL;DR: The reductions of two magnesium(II) iodide complexes with potassium metal in toluene, leading to thermally stable magnesium(I) compounds, (L)MgMg(L) in moderate yields, consistent with central Mg 2+2 units that have single, covalent magnesium-magnesium bonding interactions.
Journal ArticleDOI
A stable, neutral diborene containing a B=B double bond.
Yu-Zhong Wang,Brandon Quillian,Pingrong Wei,Chaitanya S. Wannere,Yaoming Xie,R. Bruce King,Henry F. Schaefer,Paul von Ragué Schleyer,Gregory H. Robinson +8 more
TL;DR: Compound 3 is the first structurally characterized neutral diborene and the nature of the BB double bond in 3 was delineated by DFT computations.