Reversible Insertion of a C═C Bond into Magnesium(I) Dimers: Generation of Highly Active 1,2-Dimagnesioethane Compounds

Boutland, Aaron J.; Carroll, Ashlea; Lamsfus, Carlos; Stasch, Andreas; Maron, Laurent; Jones, Cameron

doi:10.1021/jacs.7b11368

Cited by 80 publications

(71 citation statements)

References 33 publications

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“…Although reversible alkene coordination to transition metals is af undamental step often invoked in catalysis, examples of reversible reaction with main-group reagents are exceptionally rare. [42,43] Reductive elimination of norbornene from 6 is possible;t hus,a th igh temperatures 6 can act as a" masked" Al I reagent and will react with 3,3,3-trifluoropropene to yield 5. [24]…”

Section: Angewandte Chemiementioning

confidence: 99%

Reactions of Fluoroalkenes with an Aluminium(I) Complex

2018

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A series of industrially relevant fluoroalkenes react with a monomeric Al complex. These reactions break strong sp and sp C-F bonds, and result in the formation of a diverse array of organoaluminium compounds. Mechanistic studies show that two mechanisms are likely in operation: 1) direct oxidative addition of the C-F bond to Al occurs with retention of alkene stereochemistry, and 2) stepwise formation and decomposition of a metallocyclopropane intermediate occurs with inversion of alkene stereochemistry. As part of this mechanistic analysis, we have isolated the first aluminium metallocyclopropane complex from oxidative addition of an alkene to Al . Remarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming Al . Furthermore, in selected cases the organoaluminium products are susceptible toward β-fluoride elimination to yield a double C-F activation pathway.

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Section: Angewandte Chemiementioning

confidence: 99%

Reactions of Fluoroalkenes with an Aluminium(I) Complex

2018

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“…[24] More recently,J ones and co-workers reported similar dual reactivity for BDI 2 Mg 2 (DPE) in which DPE 2À bridges two Mg 2+ ions (DPE = 1,1,-diphenylethylene). [25] Also complex ( DIPeP BDI) 2 Mg 2 (C 6 H 6 )d isplays dual reactivity (Scheme 3). In reaction with tBuOH it acts as aB rønsted base giving am ixture of 1,4-and 1,3-cyclohexadiene.I n reaction with H 2 it acts as atwo-electron supply and although slow (5 days,1 00 8 8C) it gave full conversion to (BDI) 2 Mg 2 H 2 and benzene.T he crystal structure of dimeric ( DIPeP BDI) 2 Mg 2 H 2 (Figure 1b) (2) ).…”

Section: Communicationsmentioning

confidence: 99%

Low Valent Magnesium Chemistry with a Super Bulky β‐Diketiminate Ligand

et al. 2018

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The steric bulk of the well-known DIPP BDI ligand (CH[C(CH 3 )N-DIPP] 2 ,D IPP = 2,6-diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups.T his very bulky DIPeP BDI ligand could not stabilizet he radical species ( DIPeP BDI)MgC:r eduction of ( DIPeP BDI)MgI with Na gave ( DIPeP BDI) 2 Mg 2 with ar ather long Mg-Mg bond of 3.0513(8) .A ddition of TMEDAp rior to reduction gave complex ( DIPeP BDI) 2 Mg 2 (C 6 H 6 ), which could also be obtained as its THF adduct. It is speculated that combination of abulky spectator ligand and TMEDAp revents dimerization of the intermediate Mg I radical, which then reacts with the benzene solvent. Complex ( DIPeP BDI) 2 Mg 2 (C 6 H 6 ), which formally contains the anti-aromatic anion C 6 H 6 2À ,r eacted with tBuOH as aBrønsted base to 1,3-and 1,4-cyclohexadiene and with H 2 as at wo electron donor to ( DIPeP BDI) 2 Mg 2 H 2 and C 6 H 6 .I ta lso reductively cleaved the C À Fb ond in fluorobenzene and gave ( DIPeP BDI)MgPh, ( DIPeP BDI)MgF,and C 6 H 6 .

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“…[1] Despite this,i solable compounds containing s-block metal-metal bonds have only been known since 2007, [2] and all but one of these examples are three-or four-coordinate magnesium(I) dimers.I ne very case,t hese compounds are kinetically stabilized by sterically bulky N,N'-chelating,o rN,N',O-tripodal, anionic ligands,s o far confined to ar ange of b-diketiminates,aguanidinate, ad iiminophosphinate,a ne ne-diamide,a nd several diimineenolates ( Figure 1). [3][4][5][6][7] Additional examples include aremarkable mixed valence magnesium cluster anion, [Mg 16 Cp* 8 Br 4 K] À (Cp* = C 5 Me 5 À ), which was recently reported and shown by computational studies to contain no less than 27 MgÀMg bonds. [8] More than being just chemical curiosities,d imeric magnesium(I) complexes,e specially those incorporating b-diketiminate ligands,h ave been widely applied as soluble, selective,a nd safe reducing agents in ad iverse range of inorganic and organic synthetic transformations.…”

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confidence: 99%

“…As election of the amido magnesium(II) iodide compounds were crystallographically characterized, which revealed them to be either monomers or iodide bridged dimers in the solid state (see the Supporting Information). Thes tructure of one of these complexes (7)i sd epicted in Figure 2; it is the first example of ac rystallographically characterized unsolvated monodentate amido magnesium halide complex. Not surprisingly,itisaniodide bridged dimer, which exhibits several Mg···C Ph interactions of < 2.7 (S C/Mg covalent radii = 2.14 ) because of its unsolvated nature.…”

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confidence: 99%