Cycloaddition of isoselenocyanates to sodium and magnesium metallacycles

Dodonov, Vladimir A.; Kushnerova, O. A.; Rumyantcev, Roman V.; Novikov, Alexander S.; Османов, В. К.; Fedushkin, Igor L.

doi:10.1039/d1dt04366h

Cited by 12 publications

(8 citation statements)

References 94 publications

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“…Although cycloadditions of 1,3‐butadiene derivatives have been widely reported for low‐valent main‐group complexes, [25] the first cycloaddition to a 1,3‐diene with a low‐valent Ga complex has just been reported recently [26] . In addition, two other gallacyclopentenes are known [27] .…”

Section: Resultsmentioning

confidence: 99%

“…Although cycloadditions of 1,3-butadiene derivatives have been widely reported for low-valent main-group complexes, [25] the first cycloaddition to a 1,3-diene with a low-valent Ga complex has just been reported recently. [26] In addition, two other gallacyclopentenes are known. [27] In 10 Cat (Figure 4), the CÀ Ga-C bond angle in the flat gallacyclopentene-ring measures 95.5(1)°with GaÀ C1/GaÀ C2 bond lengths of 1.972(3)/1.966(3) Å.…”

Section: Reactivity Towards Dienes and White Phosphorousmentioning

confidence: 99%

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Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Dabringhaus

Heizmann

Krossing

2023

Chemistry A European J

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Although the discovery of the Ga(I) complex salt [Ga(PhF)2‐3][Al(ORF)4] (RF = C(CF3)) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent Ga(I) cations are scarce. Here, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine‐diimine pincer‐ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small‐molecules is reported. First controlled oxidative additions of the Ga(I) cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1] cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main‐group metals has previously on been reported for Ge and Sn respectively. The experimental study is supported by high level computational analysis of the in part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene.

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Section: Resultsmentioning

confidence: 99%

Section: Reactivity Towards Dienes and White Phosphorousmentioning

confidence: 99%

Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Dabringhaus

Heizmann

Krossing

2023

Chemistry A European J

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“…Moreover, the dpp-Bian ligand was shown to be able to participate in the chemical transformation by multiple noncovalent interactions. This allowed cooperative reactions even for valence-saturated metals Na + and Mg 2+ . The concept of metal–ligand cooperation was well documented for transition metal complexes; − it is much less known for main group metals and especially for lanthanides.…”

Section: Introductionmentioning

confidence: 98%

Stability and Solution Behavior of [(dpp-Bian)Ln] and [(dpp-Bian)LnX] (Ln = Yb, Tm, or Dy; X = I, F, or N₃)

et al. 2023

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Treatment of an excess of ytterbium metal with dpp-Bian {dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene} in the presence of 0.5 equiv of iodine resulted in a mixture of [(dpp-Bian)2–Yb2+(DME)2] (1) along with [YbI2(DME)2]2 and an over-reduced byproduct [(dpp-Bian)3–Yb2+I(DME)Yb2+(DME)2] (2). Oxidation of 1 with iodine is accompanied by electron transfer from the ligand to the metal atom to give [(dpp-Bian)−Yb2+I(THF)2]2 (3). Azide complexes [(dpp-Bian)2–Yb3+N3(DME)]6 (4) and [(dpp-Bian)2–Yb3+N3(THF)2]2 (5) were obtained by either oxidation of 1 with TMSN3 or salt metathesis reaction of 3 with NaN3. Fluorine complexes [(dpp-Bian)2–Yb3+F(DME)]2 (7) and [(dpp-Bian)2–Yb3+F(THF)1.5]2 (8) were obtained by oxidation of 1 with F2CCF2. Complex 3 in solution revealed reversible thermally induced intramolecular electron transfer {[(dpp-Bian)−Yb2–] ⇄ [(dpp-Bian)2–Yb3+]}. Unstable solutions of [(dpp-Bian)Dy(DME)2] (11) and [(dpp-Bian)Tm(DME)2] (12) were obtained by salt metathesis reaction of [(dpp-Bian)K2] with DyI2 or TmI2. These solutions treated with TMSN3 result in [(dpp-Bian)Dy(N)3(DME)]6 (13) and [(dpp-Bian)Tm(N)3(DME)]6 (14). The crystalline structure of azide and fluorine compounds depended on the crystallization solvent. New compounds are characterized by nuclear magnetic resonance, infrared spectroscopy, magnetic moment and differential scanning calorimetry measurements, and elemental and X-ray diffraction analysis. Solution transitions were probed by absorption spectroscopy.

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“…14 Ligand-centered cooperative reactivity of α-diimines can arise either from their ability to directly form bonds with substrates 27,29,30 or electron transfer to the metal centers (Scheme 1). 28,31 These processes may significantly regulate the reactivity of metal centers, 29 even for the commonly known unreactive Na + and Mg 2+ , 30 and may facilitate the two-electron transformations of Ga 2+ . 31 The dialumanes […”

Section: ■ Introductionmentioning

confidence: 99%

“…We have been exploring the reactivities of α-diimine-ligated low-valent group 13 metal (Al, Ga) compounds toward a variety of organic substrates, wherein the redox non-innocent α-diimine ligands can also participate in the reactions. ,− Ligand-centered cooperative reactivity of α-diimines can arise either from their ability to directly form bonds with substrates ,, or electron transfer to the metal centers (Scheme ). , These processes may significantly regulate the reactivity of metal centers, even for the commonly known unreactive Na + and Mg 2+ , and may facilitate the two-electron transformations of Ga 2+ …”

Section: Introductionmentioning

confidence: 99%

Reactions of Low-Valent Gallium Species with Organic Azides: Formation of Imido-, Azoimido-, and Tetrazene Complexes

et al. 2023

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The reactivity of two α-diimine-ligated digallanes, [L2–Ga–GaL2–] (La = [(2,6-iPr2C6H3)NC(CH3)]2, dpp-dad, 1; Lb = 1,2-[(2,6-iPr2C6H3)NC]2C10H6, dpp-bian, 2), and a gallylene, [(La)2–GaNa(THF)3] (3), toward organic azides was studied. Reaction of digallane 1 or 2 with trimethylsilyl azide (Me3SiN3), 2-azido-benzonitrile (2-CNC6H4N3), or tosylazide (TosN3) results in imido-bridged complexes, [(La)· –Ga(μ-NSiMe3)2Ga(La)· –] (4) [(Lb)· –Ga(μ-NSiMe3)2Ga(Lb)· –] (5), [(Lb)· –Ga(μ-2-CNC6H4N)2Ga(Lb)· –] (6), and [(Lb)· –Ga(μ-NTos)2Ga(Lb)· –] (7), with elimination of dinitrogen. Treatment of 1 or 2 with 1-adamantyl azide (1-AdN3), on the other hand, affords the unsymmetrical dinuclear complexes [(La)· –Ga(NAd)(N3Ad)Ga(La)· –] (8) and [(Lb)· –Ga(NAd)(N3Ad)Ga(Lb)· –] (9), which contain both imido and triazene bridges. Different from the Ga(II) complexes 1 and 2, the reactions of Ga(I) species 3 with benzylazide or trimethylsilyl azide result in the tetrazene complex {Na(THF)}2[(La)2–Ga(benzyl-N4-benzyl)]2 (10) and amide complex {Na(THF)4}[(La)2–Ga(NHSiMe3)(benzyl)] (11). It is likely that these latter transformations proceed via the transient formation of the corresponding GaN imide complex, which undergoes either cycloaddition with a second azide (to form 10) or activation of the C–H bond of methyl in one solvent toluene molecule (to yield 11).

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Cycloaddition of isoselenocyanates to sodium and magnesium metallacycles

Cited by 12 publications

References 94 publications

Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Stability and Solution Behavior of [(dpp-Bian)Ln] and [(dpp-Bian)LnX] (Ln = Yb, Tm, or Dy; X = I, F, or N₃)

Reactions of Low-Valent Gallium Species with Organic Azides: Formation of Imido-, Azoimido-, and Tetrazene Complexes

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Cycloaddition of isoselenocyanates to sodium and magnesium metallacycles

Cited by 12 publications

References 94 publications

Activation of the GaI Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P4

Activation of the GaI Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P4

Stability and Solution Behavior of [(dpp-Bian)Ln] and [(dpp-Bian)LnX] (Ln = Yb, Tm, or Dy; X = I, F, or N3)

Reactions of Low-Valent Gallium Species with Organic Azides: Formation of Imido-, Azoimido-, and Tetrazene Complexes

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Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Activation of the Ga^I Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P₄

Stability and Solution Behavior of [(dpp-Bian)Ln] and [(dpp-Bian)LnX] (Ln = Yb, Tm, or Dy; X = I, F, or N₃)