Trimethylsilyl‐substituted triazole‐based ligand for copper‐mediated single‐electron transfer living radical polymerization of methyl methacrylate

Sangtrirutnugul, Preeyanuch; Wised, Kritdikul; Maisopa, Purmpoon; Trongsiriwat, Nisalak; Tangboriboonrat, Pramuan; Reutrakul, Vichai

doi:10.1002/pi.4719

Cited by 7 publications

(5 citation statements)

References 55 publications

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“…Its tetradentate binding cavity was able to completely envelope the Cu + center . Recently, a tert ‐butyl analogue of tbta ( ttta ) displayed even better catalytic activity than that of tbta . Because of the poor solubility of tbta in aqueous media, more polar analogues of this ligand were prepared ( thpta , 25a , and 25b ; Fig.…”

Section: Triazoles In Functional Materials and Sensorsmentioning

confidence: 99%

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

Lauko

Kouwer

Rowan

2016

Journal of Heterocyclic Chem

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The heterocyclic family of azoles have recently become one of the most widely used members of the N‐heterocycles; the most prominent one being 1H‐1,2,3‐triazole and its derivatives. The sudden growth of interest in this structural motif was sparked by the advent of click chemistry, first described in the early 2000s. From the early days of click chemistry, when the accessibility of triazoles made them into one of the most versatile linkers, interest has slowly turned to the use of triazoles as functional building blocks. The presence of multiple N‐coordination sites and a highly polarized carbon atom allows for metal coordination and the complexation of anions by both hydrogen and halogen bonding. Exploitation of these multiple binding sites makes it possible for triazoles to be used in various functional materials, such as metallic and anionic sensors. More recently, triazoles have also shown their potential in catalytic systems, thus increasing their impact far beyond the initial purpose of click chemistry. This report gives an overview of the structure, functionalities, and use of triazoles with a focus on their use in catalytic systems.

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Section: Triazoles In Functional Materials and Sensorsmentioning

confidence: 99%

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

Lauko

Kouwer

Rowan

2016

Journal of Heterocyclic Chem

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“…The Cu(I) catalyzed “click” reaction, which selectively produces only one regioisomer of the resulting 1,2,3-triazoles, , has become an important route to novel ligands in coordination and organometallic chemistry. − Taking advantage of this modular synthetic route, a battery of novel ligands, “tuned to the occasion”, have been synthesized. Their resulting metal complexes, such as of Ru(II), − have been probed with respect to their function in photo and redox chemistry and in homogeneous catalysis. − Among our interests is the development of metal complexes with tunable electronic structures, with possible applications as single ion magnets. , In particular, we have recently discovered that click-derived tripodal ligands can deliver special features to their metal complexes with respect to magnetic properties. The magnetic anisotropy of Ni(II) and Co(II) complexes with such ligands has been investigated.…”

Section: Introductionmentioning

confidence: 99%

Tuning Magnetic Anisotropy Through Ligand Substitution in Five-Coordinate Co(II) Complexes

et al. 2017

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Understanding the origin of magnetic anisotropy and having the ability to tune it are essential needs of the rapidly developing field of molecular magnetism. Such attempts at determining the origin of magnetic anisotropy and its tuning are still relatively infrequent. One candidate for such attempts are mononuclear Co(II) complexes, some of which have recently been shown to possess slow relaxation of their magnetization. In this contribution we present four different five-coordinated Co(II) complexes, 1-4, that contain two different "click" derived tetradentate tripodal ligands and either Cl or NCS as an additional, axial ligand. The geometric structures of all four complexes are very similar. Despite this, major differences are observed in their electronic structures and hence in their magnetic properties as well. A combination of temperature dependent susceptibility measurements and high-frequency and -field EPR (HFEPR) spectroscopy was used to accurately determine the magnetic properties of these complexes, expressed through the spin Hamiltonian parameters: g-values and zero-field splitting (ZFS) parameters D and E. A combination of optical d-d absorption spectra together with ligand field theory was used to determine the B and Dq values of the complexes. Additionally, state of the art quantum chemical calculations were applied to obtain bonding parameters and to determine the origin of magnetic anisotropy in 1-4. This combined approach showed that the D values in these complexes are in the range from -9 to +9 cm. Correlations have been drawn between the bonding nature of the ligands and the magnitude and sign of D. These results will thus have consequences for generating novel Co(II) complexes with tunable magnetic anisotropy and hence contribute to the field of molecular magnetism.

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“…15 Tripodal triazole-based ligands, e.g. 16 TBTA and derivatives (Chart 2), were shown to act as flexible ligands with different coordination modes. 17 In combination with the ease of substituent exchange, this flexibility renders these compounds an ideal ligand class for the investigation of substituent effects on structural and electronic properties of metal-azido complexes.…”

Section: Introductionmentioning

confidence: 99%

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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Trimethylsilyl‐substituted triazole‐based ligand for copper‐mediated single‐electron transfer living radical polymerization of methyl methacrylate

Cited by 7 publications

References 55 publications

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

Tuning Magnetic Anisotropy Through Ligand Substitution in Five-Coordinate Co(II) 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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Trimethylsilyl‐substituted triazole‐based ligand for copper‐mediated single‐electron transfer living radical polymerization of methyl methacrylate

Cited by 7 publications

References 55 publications

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

1H‐1,2,3‐Triazole: From Structure to Function and Catalysis

Tuning Magnetic Anisotropy Through Ligand Substitution in Five-Coordinate Co(II) 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