Two‐Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands

Boutland, Aaron J.; Dange, Deepak; Stasch, Andreas; Maron, Laurent; Jones, Cameron

doi:10.1002/ange.201604362

Cited by 19 publications

(3 citation statements)

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“…4c,d Notwithstanding this, and to the best of our knowledge, there have been no reports of crystallographically characterized oxocarbon anions derived from s-block metal reductions of CO. 8 Since their discovery in 2007, 9 we have extensively developed the reduction chemistry of isolable magnesium(I) compounds, [(L)Mg−Mg(L)] (L = bulky guanidinate, βdiketiminate, amide, etc. ), 10,11 and we believe they could prove useful as selective and soluble reductants for oxocarbon anion formations. However, we have previously shown that these compounds are unreactive toward CO, though when hydrogenated the generated magnesium hydride complexes, [{( Ar Nacnac)Mg(μ-H)} 2 ] ( Ar Nacnac = [(ArNCMe) 2 CH] − , Ar = 2,6-diethylphenyl (Dep), or 2,6-diisopropylphenyl (Dip)), do couple CO to selectively give an ethylenediolate, [{( Dip Nacnac)Mg} 2 (μ-O 2 C 2 H 2 )], or an unprecedented cyclopropanetriolate compound, [{( Dep Nacnac)Mg} 3 (μ-O 3 C 3 H 3 )], depending on the size of the β-diketiminate ligand employed.…”

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confidence: 85%

Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

et al. 2019

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This study details syntheses of unsymmetrical magnesium(I)−adduct complexes, [( Ar Nacnac)-(D)Mg−Mg( Ar Nacnac)] ( Ar Nacnac = [(ArNC-Me) 2 CH] − ), Ar = xylyl (Xyl), mesityl (Mes), 2,6diethylphenyl (Dep), or 2,6-diisopropylphenyl (Dip); D = N-heterocyclic carbene or 4-dimethylaminopyridine, DMAP), which X-ray crystallographic studies show to have markedly elongated Mg−Mg bonds. Two of these highly reactive species are shown to reductively trimerize CO to yield rare crystallographically characterized examples of the planar, aromatic deltate dianion, incorporated in the complexes [{( Dip Nacnac)(D)Mg(μ-C 3 O 3 )Mg( Dip Nacnac)} 2 ] (D = DMAP or :C{N(Me)C-(Me)} 2 ). DFT calculations suggest that these complexes form via stepwise two-electron reductions of three CO molecules, resulting in the formation of three C−C bonds within the cyclic deltate unit. This work highlights the utility of activated magnesium(I) adduct complexes as soluble organometallic models for the study of reductive C−C bond-forming events in, for example, the heterogeneously catalyzed Fischer−Tropsch process.

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Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

et al. 2019

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“…Notably, there appear to be no previous reports on molecular compounds that contain such a trinuclear Mg3I4 2+ or even an MgI4 2− fragment [17]. However, the terminal [(Ar2N3)MgI2] 2− fragments may be compared with related dimeric complexes of the general composition [(L)Mg-μ-I2Mg(L)] where L represents bulky amido, diketiminato, diiminophosphinato or guanidinato ligands [18][19][20][21][22]. In 3a and 3b, the coordination spheres of the central magnesium atoms feature distorted tetrahedral geometries with I-Mg2-I angles in the range 96.24(6)°-120.55(8)° (3a) and 98.09(4)°-116.70(5)° (3b), respectively.…”

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confidence: 99%

“…where L represents bulky amido, diketiminato, diiminophosphinato or guanidinato ligands [18][19][20][21][22]. In 3a and 3b, the coordination spheres of the central magnesium atoms feature distorted tetrahedral geometries with I-Mg2-I angles in the range 96.24 (6) • -120.55 (8) • (3a) and 98.09(4) • -116.70 (5) • (3b), respectively.…”

Section: Structural Studiesmentioning

confidence: 99%

Hetero- and Homoleptic Magnesium Triazenides

Vinduš

Niemeyer

2017

Inorganics

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Using monoanionic triazenide ligands derived from biphenyl and m-terphenyl substituted triazenes Dmp(Tph)N 3 H (1a), (Me 4 Ter) 2 N 3 H (1b) or Dmp(Mph)N 3 H (1c) (Dmp = 2,6-Mes 2 C 6 H 3 with Mes = 2,4,6-Me 3 C 6 H 2 ; Me 4 Ter = 2,6-(3,5-Me 2 C 6 H 3 ) 2 C 6 H 3 ; Mph = 2-MesC 6 H 4 ; Tph = 2-TripC 6 H 4 with Trip = 2,4,6-i-Pr 3 C 6 H 2 ), several magnesium triazenides were synthesized. Heteroleptic complexes [Mg(N 3 Ar 2 )I(OEt 2 )] (Ar 2 = Dmp/Tph (2a), (Me 4 Ter) 2 (2b) were obtained from metalation of the corresponding triazenes with di-n-butylmagnesium followed by reaction with iodine in diethyl ether as the solvent in high yields. Replacing diethyl ether by n-heptane afforded trinuclear compounds [Mg 3 (N 3 Ar 2 ) 2 I 4 ] (3a, 3b) in low yields in which a central MgI 2 fragment is coordinated by two iodomagnesium triazenide moieties. Two unsolvated homoleptic magnesium compounds [Mg(N 3 Ar 2 ) 2 ] (4b, 4c) were obtained from di-n-butylmagnesium and triazenes 1b or 1c in a 1:2 ratio. Depending on the nature of the substituents, the magnesium center either shows the expected tetrahedral or a rather unusual square planar coordination.

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Isolierung und Charakterisierung von kristallinen, neutralen Diboran(4)‐Radikalen

et al. 2018

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Bei der Umsetzung von Diaryldihalogendiboranen(4) mit Bis(amidinato)‐ und Bis(guanidinato)silylenen wurden die ersten neutralen Diboran‐zentrierten Radikale erhalten. Diese formal nicht‐aromatischen 5π‐Elektronen‐Systeme sind sowohl im Festkörper, als auch in Lösung stabil und wurden mittels Einkristallstrukturanalyse, hochauflösender Massenspektrometrie und ESR‐Spektroskopie charakterisiert. Die Reaktivität eines dieser Radikale mit dem Oxidationsmittel 1,4‐Benzoquinon führte zur Ringöffnung und B‐O‐Bindungsbildung.

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Two‐Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands

Cited by 19 publications

References 28 publications

Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

Hetero- and Homoleptic Magnesium Triazenides

Isolierung und Charakterisierung von kristallinen, neutralen Diboran(4)‐Radikalen

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