2,6-Bis(benzimidazol-2-yl)pyridine complexes of group 14 elements

Swidan, Ala’aeddeen; Onge, P. Blake J. St.; Binder, Justin F.; Suter, Riccardo; Burford, Neil; Macdonald, Charles L. B.

doi:10.1039/c9dt00995g

Cited by 22 publications

(19 citation statements)

References 53 publications

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“…The structure is in line with observations deduced from the NMR analysis and no exchange equilibrium in the coordination [10] Scheme 2. Reaction of dab 2 py with MeLi.…”

Section: Reaction Of Dab 2 Py With Melisupporting

confidence: 88%

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Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Rommel

Fix

Böttcher

2022

Zeitschrift anorg allge chemie

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Dedicated to Professor Caroline Röhr on the occasion of her 60 th birthday.The reactivity of 2,6-bis(diazaboryl)pyridine (dab 2 py) with the metal alkyls MeLi, Et 2 Zn and n-Bu 2 Mg is reported. In all reactions, the alkylation of one boron atom of dab 2 py was observed to yield a new type of anionic pyridine ligand, which forms the respective adducts with [Li(OEt 2 )] + , [ZnEt] + or [Mg(n-Bu)] + . The alkylation of the boron atom results in a tetrahedral geometry, which allows for both amine nitrogen atoms to participate in the coordination. The products are highly soluble in all common solvents including alkanes. The reactivity is compared with the one already reported for unsubstituted pyridine, which is alkylated at the 2-position by treatment with MeLi. The reaction of these metal alkyls with the popular terdentate 2,6-diiminopyridine ligand (DIMPY) were previously reported to yield N-alkylated anionic ligands, which subsequently undergo alkyl-migration or deprotonation reactions. Single crystal XRD was performed on the products obtained from the reaction with MeLi and Et 2 Zn. Attempts to grow crystals for the respective magnesium alkyl complex in a dry ice box yielded a dinuclear complex bridged by two valerate groups instead.

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“…The structure is in line with observations deduced from the NMR analysis and no exchange equilibrium in the coordination [10] Scheme 2. Reaction of dab 2 py with MeLi.…”

Section: Reaction Of Dab 2 Py With Melisupporting

confidence: 88%

“…Left: A rapid exchange between all four N dab -atoms in solution observed for [(dab 2 py)AlX 2 ] + (X=Br). Right: Rigid terdentate coordination of the DIMPY-ligand for [(DIMPY)AlX 2 ] + (X=Cl) [10].…”

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confidence: 99%

Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Rommel

Fix

Böttcher

2022

Zeitschrift anorg allge chemie

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“… 13 − 17 Self-ionization can also be induced by ligands, and the compounds [TiF 2 ([15]crown-5)][Ti 4 F 18 ], [AuCl 2 py 2 ][AuCl 4 ]·2[AuCl 3 py], [NbF 4 (Me 2 S) 4 ][NbF 6 ], and [(L Dipp ) 2 SbF 2 ][SbF 4 ] or [Ta(N 3 ) 4 (1,10-phen) 2 ][M(N 3 ) 6 ], [Be 2 I 2 (dmf) 4 ][Be 2 I 6 ], and [BePh(12-crown-4)][BePh 3 ] serve as examples. 18 − 29…”

Section: Introductionmentioning

confidence: 99%

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX₄ (X = Cl, Br, I)/Ethyl Acetate System

et al. 2022

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The reaction of the uranium(IV) halides UCl 4 , UBr 4 , or UI 4 with ethyl acetate (EtOAc) leads to the formation of the complexes [UX 3 (EtOAc) 4 ][UX 5 (EtOAc)] (X = Cl, Br) or [UI 4 (EtOAc) 3 ]. Thus, both UCl 4 and UBr 4 show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX 3 (EtOAc) 4 ] + cation and a distorted octahedral [UX 5 (EtOAc)] − anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl 3 (EtOAc) 4 ][UCl 5 (EtOAc)] crystallizes in the orthorhombic crystal system, space group P 2 1 2 1 2 1 at 250 K, the bromide compound crystallizes in the monoclinic crystal system, P 12 1 / n 1 at 100 K. Unexpectedly, UI 4 does not show self-ionization but forms [UI 4 (EtOAc) 3 ] molecules, which crystallize in the monoclinic crystal system, P 2 1 / c , at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.

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“…A relatively small number of structures in which the N atom of an azabenzene moiety coordinates intermolecularly to an Sn(II) center have been deposited in the Cambridge Structural Database (CSD) 23 so far (Section S1). The vast majority of the structures carry ligands which are either substituted azabenzenes 24–28 or polycyclic molecules possessing an azabenzene moiety 28–33 . There has been a slowly growing interest in the complexes formed by simple stannylenes and unsubstituted azabenzenes 34–43 .…”

Section: Introductionmentioning

confidence: 99%

“…The vast majority of the structures carry ligands which are either substituted azabenzenes [24][25][26][27][28] or polycyclic molecules possessing an azabenzene moiety. [28][29][30][31][32][33] There has been a slowly growing interest in the complexes formed by simple stannylenes and unsubstituted azabenzenes. [34][35][36][37][38][39][40][41][42][43] However, these studies exclusively address stannylene complexes bearing pyridine donor ligands.…”

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confidence: 99%

Tuning the metal–ligand bond in theσ‐complexes of stannylenes and azabenzenes

2021

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The metal-ligand bond in a set of 60 σ-complexes has been investigated by electronic structure computations. These σ-complexes originate from the unique combination of 12 stannylenes (SnX 2 ) with five azabenzene ligands (pyridine, pyrazine, pyrimidine, pyridazine, and s-triazine), where the nitrogen center of the ligand acts as σ-donor and the tin(II) center as σ-acceptor in a 1:1 fashion. The Sn N bond and the total interaction between the stannylene and azabenzene moieties of the σ-complexes are characterized in depth to relate the Sn N strength to the substitution pattern at SnX 2 and to the number and the positioning of N atoms in the azabenzenes. Such X substituents as (iso)cyano and trifluoromethyl groups enhance the interaction strength, while the presence of alkyl, phenyl, and silyl substituents in SnX 2 diminishes the stability of σ-complexes. A gradual weakening of the total interaction is associated with the growing number of N atoms in the azabenzenes, while the N-atom positioning in pyridazine is particularly effective in strengthening the interaction with stannylenes. Variations in the Sn N bond strength usually follow those in the total interaction between the moieties but the interacting quantum atoms picture of Sn N reveals certain intriguing exceptions.

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2,6-Bis(benzimidazol-2-yl)pyridine complexes of group 14 elements

Abstract: Variants of the 2,6-bis(benzimidazol-2-yl)pyridine ligand are used to synthesize novel group 14 complexes of germanium and tin. The salts are characterized by X-ray crystallography, NMR, UV-vis, and the Lewis acidity of some examples are probed.

Cited by 22 publications

References 53 publications

Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX₄ (X = Cl, Br, I)/Ethyl Acetate System

Tuning the metal–ligand bond in theσ‐complexes of stannylenes and azabenzenes

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2,6-Bis(benzimidazol-2-yl)pyridine complexes of group 14 elements

Abstract: Variants of the 2,6-bis(benzimidazol-2-yl)pyridine ligand are used to synthesize novel group 14 complexes of germanium and tin. The salts are characterized by X-ray crystallography, NMR, UV-vis, and the Lewis acidity of some examples are probed.

Cited by 22 publications

References 53 publications

Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Reaction of 2,6‐Bis(diazaboryl)pyridine with Alkyls of Lithium, Zinc and Magnesium

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX4 (X = Cl, Br, I)/Ethyl Acetate System

Tuning the metal–ligand bond in theσ‐complexes of stannylenes and azabenzenes

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Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX₄ (X = Cl, Br, I)/Ethyl Acetate System