Hybrid Pyrazolyl-1,2,3-Triazolyl Tripodal Tetraamine Ligands: Click Synthesis and Cobalt(III) Complexes

Cubanski, John R.; Reish, Matthew E.; Blackman, Allan G.; Steel, Peter J.; Gordon, Keith C.; McMorran, David A.; Crowley, James D.

doi:10.1071/ch14700

Cited by 4 publications

(2 citation statements)

References 25 publications

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“…[22][23][24][25][26][27] The tuning of electronic and steric properties of the ligands becomes reasonably straightforward with this modular synthesis. The resulting substituted 1,2,3-triazoles have been extensively used in coordination chemistry as ligands, and the resulting metal complexes have been investigated towards their biological activity [28][29][30][31][32][33][34] as well as for their photochemical, [35][36][37][38] catalytic 36,[39][40][41][42][43][44][45] and electrochemical properties. 35,37,46 The click-derived tripodal ligand tbta (tris[(1-benzyl-1H-1,2,3-triazol-4yl)methyl]amine) (Fig.…”

Section: Introductionmentioning

confidence: 99%

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

et al. 2022

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“…Substituted 1,2,3-triazoles derived from the Cu(I) catalyzed “click” reaction between azides and alkynes − have been extensively used as ligands in coordination chemistry in recent years. − In that context, we have made use of the tripodal ligand tris[(1-benzyl-1 H -1,2,3-triazol-4-yl)methyl]amine, TBTA (Figure ), and reported on its Co(II) and Fe(II) complexes that display magnetic bistability, , show metal oxidation state dependent coordination changes, and are precatalysts for ethylene polymerization . Mononuclear [Co(TBTA)(N 3 )] + was reported as well and its electronic structure, particularly with a focus on the ligand field of the N 3 – ligand, was investigated .…”

Section: Introductionmentioning

confidence: 99%

Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo- and Heterodinuclear Cobalt-Azido Complexes

Sommer¹,

Marx

Schweinfurth³

et al. 2016

Inorg. Chem.

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The azide anion is widely used as a ligand in coordination chemistry. Despite its ubiquitous presence, controlled synthesis of azido complexes remains a challenging task. Making use of click-derived tripodal ligands, we present here various coordination motifs of the azido ligands, the formation of which appears to be controlled by the peripheral substituents on the tripodal ligands with otherwise identical structure of the coordination moieties. Thus, the flexible benzyl substituents on the tripodal ligand TBTA led to the formation of the first example of an unsupported and solely μ-azido-bridged dicobalt(II) complex. The more rigid phenyl substituents on the TPTA ligand deliver an unsupported and solely μ-azido-bridged dicobalt(II) complex. Bulky diisopropylphenyl substituents on the TDTA ligand deliver a doubly μ-azido-bridged dicobalt(II) complex. Intriguingly, the mononuclear copper(II) complex [Cu(TBTA)N] is an excellent synthon for generating mixed dinuclear complexes of the form [(TBTA)Co(μ-N)Cu(TBTA)] or [(TBTA)Cu(μ-N)Cu(TPTA)], both of which contain a single unsupported μ-N as a bridge. To the best of our knowledge, these are also the first examples of mixed dinuclear complexes with a μ-N monoazido bridge. All complexes were crystallographically characterized, and selected examples were probed via magnetometry and high-field EPR spectroscopy to elucidate the electronic structures of these complexes and the nature of magnetic coupling in the various azido-bridged complexes. These results thus prove the power of click-tripodal ligands in generating hitherto unknown chemical structures and properties.

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Structural snapshots in the copper(ii) induced azide–nitrile cycloaddition: effects of peripheral ligand substituents on the formation of unsupported μ_1,1-azido vs. μ_1,4-tetrazolato bridged complexes

et al. 2016

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The azido ligand is widely used in coordination chemistry both as a ligand and as a metal-bound reactant. Its role as a bridge for magnetic exchange coupling has attracted a lot of attention in polynuclear metal complexes. However, only a very limited number of complexes are known in which a single azide anion, particularly in the μ-mode, is the only unsupported connection between two metal centers. We present here a series of copper(ii)-azido complexes with amine anchored, triazole-based tripodal ligands containing varying substituents. In the mononuclear copper-azido complexes there is only a negligible effect of these substituents on the structure of the metal complexes. However, the substituents seem to play a decisive role in the type and formation of the dinuclear complexes. Using the tripodal ligand TBTA with flexible benzyl substituents resulted in a rare example of an unsupported and solely μ-azido-bridged dinuclear complex. The use of the TDTA ligand with 2,6-diisopropylphenyl moieties as rigid and sterically demanding substituents resulted in the formation of a scarce example of a solely μ-tetrazolato-bridged dinuclear complex by in situ cycloaddition between the azide and solvent nitrile. This observation of a reaction of unactivated aliphatic nitrile with the azide anion at room temperature is very unusual. The isolation and characterization (by means of X-ray diffraction) of intermediates allows for mechanistic insights into the cycloaddition reaction. The isolated bridges in both dinuclear complexes render them ideal model compounds for the investigation of the magnetic exchange mediated by these ligands usually employed in polynuclear complexes and frameworks together with additional bridging ligands. Magnetic measurements and broken-symmetry DFT calculations were used to shed light on the magnetic exchange revealing weak and moderate antiferromagnetic exchange for the azide and tetrazolate, respectively.

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Hybrid Pyrazolyl-1,2,3-Triazolyl Tripodal Tetraamine Ligands: Click Synthesis and Cobalt(III) Complexes

Cited by 4 publications

References 25 publications

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo- and Heterodinuclear Cobalt-Azido Complexes

Structural snapshots in the copper(ii) induced azide–nitrile cycloaddition: effects of peripheral ligand substituents on the formation of unsupported μ_1,1-azido vs. μ_1,4-tetrazolato bridged complexes

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Hybrid Pyrazolyl-1,2,3-Triazolyl Tripodal Tetraamine Ligands: Click Synthesis and Cobalt(III) Complexes

Cited by 4 publications

References 25 publications

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes

Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo- and Heterodinuclear Cobalt-Azido Complexes

Structural snapshots in the copper(ii) induced azide–nitrile cycloaddition: effects of peripheral ligand substituents on the formation of unsupported μ1,1-azido vs. μ1,4-tetrazolato bridged complexes

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Structural snapshots in the copper(ii) induced azide–nitrile cycloaddition: effects of peripheral ligand substituents on the formation of unsupported μ_1,1-azido vs. μ_1,4-tetrazolato bridged complexes