Coordination Chemistry of Bulky Aminopryridinates with Main Group and Transition Metals

Noor, Awal

doi:10.1007/s41061-020-00320-8

Cited by 9 publications

(8 citation statements)

References 74 publications

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“…Sterically demanding N-ligands [1][2][3][4][5][6] have been driving advances in numerous areas of chemical research. In main group chemistry, for example, the introduction of sterically demanding N-ligands and related species has led to the discovery of compound classes with low coordination numbers in a variety of oxidation states, which stabilised molecular entities in unusual bonding modes that were found to show unique properties and novel reactivities [7][8][9].…”

Section: Introductionmentioning

confidence: 99%

A Convenient One-Pot Synthesis of a Sterically Demanding Aniline from Aryllithium Using Trimethylsilyl Azide, Conversion to β-Diketimines and Synthesis of a β-Diketiminate Magnesium Hydride Complex

Demidov,

Grebogi,

Bourne

et al. 2023

Molecules

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This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr3-C6H2) with trimethylsilyl azide afforded the silyltriazene TripN2N(SiMe3)2 in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH2 in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip2-C6H3) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe3)Li in parallel, which afforded TerN(SiMe3)H after workup, and can be deprotected under acidic conditions to form the aniline TerNH2. TripNH2 was furthermore converted to the sterically demanding β-diketimines RTripnacnacH (=HC{RCN(Trip)}2H), with R = Me, Et and iPr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [{(iPrTripnacnac)MgH}2], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties.

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Section: Introductionmentioning

confidence: 99%

A Convenient One-Pot Synthesis of a Sterically Demanding Aniline from Aryllithium Using Trimethylsilyl Azide, Conversion to β-Diketimines and Synthesis of a β-Diketiminate Magnesium Hydride Complex

Demidov,

Grebogi,

Bourne

et al. 2023

Molecules

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“…Much research on the extractant synthesis demonstrated that nitrogen atoms in a pyridine group possessed an excellent binding selectivity for transition metals. − Savchuk et al found that 2,6-bis(imidazole-2-yl) pyridine can selectively complex transition metals. Mautner et al used four different pyridine-N-oxides to complex Mn 2+ in aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

Improving Extraction Performance of D2EHPA for Impurities Removal from Spent Lithium-Ion Batteries Leaching Solution by TPC[4]

Zeng

et al. 2022

ACS Sustainable Chem. Eng.

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To reduce reagent consumption, wastewater discharge, and production cost of Mn 2+ recovery and impurities (Zn 2+ /Cu 2+ /Ca 2+ ) removal from an acid leaching solution of spent lithium-ion batteries, a mixed extractant (TPC[4]+D2EHPA) was synthesized, and the extraction performances for Mn 2+ and impurities were systematically investigated. The synthesis experimental results demonstrated that TPC[4] can be synthesized in a simple and high yield way with cheap raw materials. Extraction tests indicated that the separation coefficients of Mn 2+ , Cu 2+ , and Zn 2+ to Ni 2+ and Co 2+ by D2EHPA were significantly enlarged by the addition of TPC [4], which can mainly be attributed to the enhancement in the differences of binding abilities for cationic complexes with different sizes. Furthermore, the loading capacities of Mn 2+ and impurities (Cu 2+ , Zn 2+ ) were also enlarged, and the stripping of these cations could easily be achieved with dilute acid. Compared with traditional Mn 2+ and an impurities extraction process with D2EHPA alone, the addition of TPC[4] saved about 10.36% of the saponification alkali (NaOH), 10.36% of the washing acid (H 2 SO 4 ), ∼20% of the washing water, and more than 4.56% of the organic loss. From both economic and environmental perspectives, the mixed solvent of D2EHPA+TPC[4] is an excellent application prospect.

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“…The coordination chemistry of 2-aminopyridines is a highly popular area of research mainly due to their easy accessibility as well as steric and electronic versatility [1,2]. The ligand class has shown rich coordination chemistry with predominantly chelating (common) and bridging coordination modes (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, η 1 -bonding via the amine nitrogen is rather exceptional and may occur only if coordination at the p N-donor site is not feasible for steric reasons. Since the introduction of bulky versions of these ligands in 2004, they hav successfully used to stabilize not only p-block and early transition metals but a thanides with good control of metal to ligand stoichiometry [2,4,5]. Surprisingl coordination chemistry with late transition metals has not been explored yet.…”

Section: Introductionmentioning

confidence: 99%

“…Des fact that aminopyridines have been investigated for years, little is known abo aminopyridinates [6]. Among late transition metals, the versatile coordination ch of iron in different oxidation states with a variety of chelating ligands has alw Since the introduction of bulky versions of these ligands in 2004, they have been successfully used to stabilize not only p-block and early transition metals but also lanthanides with good control of metal to ligand stoichiometry [2,4,5]. Surprisingly, their coordination chemistry with late transition metals has not been explored yet.…”

Section: Introductionmentioning

confidence: 99%

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Crystallographic Evidence of η1-Coordination of Bulky Aminopyridine in Halide-Containing Iron (II) Complexes

Noor

2022

Crystals

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Reaction of N-(2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridine-2-yl]-amine (ApH) in equimolar ratio with anhydrous FeBr2 and FeI2 in tetrahydrofuran (THF) afforded, after workup in toluene, the first examples of mono(aminopyridine) Fe(II) complexes, [ApHFeBr(µ-Br)]2 (1) and [ApHFeI2(thf)] (2), respectively. X-ray analysis shows 1 to be dimeric, whereas compound 2 is monomeric. In both cases, aminopyridine ligands show rare η1-coordination to Fe through pyridine nitrogen atom. Compound 1 exhibits intramolecular N–H⋯Br hydrogen bonds [3.363 Å] with an N–H⋯Br angle of 158.84°. Hirshfeld surface and fingerprint plots identify the significant intermolecular interactions in the crystal network. Both compounds crystallized in the monoclinic space group. For compound 1, C2/c, the cell parameters are: a = 25.5750(5) Å, b = 10.5150(5) Å, c = 18.9610(8) Å, β = 97.892(5)°, V = 5050.7(3) A3, Z = 4. For compound 2, P21/c, the cell parameters are: a = 10.3180(7) Å, b = 16.1080(10) Å, c = 18.6580(11) Å, β = 102.038(5)°, V = 3032.8(3) A3, Z = 4.

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Coordination Chemistry of Bulky Aminopryridinates with Main Group and Transition Metals

Cited by 9 publications

References 74 publications

A Convenient One-Pot Synthesis of a Sterically Demanding Aniline from Aryllithium Using Trimethylsilyl Azide, Conversion to β-Diketimines and Synthesis of a β-Diketiminate Magnesium Hydride Complex

A Convenient One-Pot Synthesis of a Sterically Demanding Aniline from Aryllithium Using Trimethylsilyl Azide, Conversion to β-Diketimines and Synthesis of a β-Diketiminate Magnesium Hydride Complex

Improving Extraction Performance of D2EHPA for Impurities Removal from Spent Lithium-Ion Batteries Leaching Solution by TPC[4]

Crystallographic Evidence of η1-Coordination of Bulky Aminopyridine in Halide-Containing Iron (II) Complexes

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