Coordination chemistry of tris(azolyl)phosphines

Tazelaar, Cornelis G. J.; Slootweg, J. Chris; Lammertsma, Koop

doi:10.1016/j.ccr.2017.10.024

Cited by 12 publications

(5 citation statements)

References 144 publications

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“…Tripodal ligands have been widely used in coordination chemistry of metals across the entire periodic table. − The high modularity of tripodal ligands allows fine-tuning of their electronic and steric effects, which leads to novel structures , and unprecedented reactivity. − They have also found applications in areas as diverse as medical imaging and therapy and crystal engineering . The architecture of tripodal ligands features three neutral or anionic donor arms linked by an anchor group.…”

Section: Introductionmentioning

confidence: 99%

Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor

et al. 2021

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A new tripodal tris(amido) ligand system featuring an arene anchor was developed and applied to the coordination chemistry of rare earth metals. Two tris(amido) ligands with a 1,3,5-triphenylbenzene backbone were prepared in two steps from commercially available reagents on a gram scale. Salt metathesis and alkane elimination reactions were exploited to prepare mononuclear rare earth metal complexes in moderate to good yields. For salt metathesis reactions, while metal tribromides yielded neutral metal tris(amido) complexes, metal trichlorides led to the formation of ate complexes with an additional chloride bound to the metal center. The new compounds were characterized by X-ray crystallography, elemental analysis, and 1H and 13C nuclear magnetic resonance spectroscopy. The rare earth metal complexes exhibit a trigonal planar coordination geometry for the [MN3] fragment in the solid state rather than a trigonal pyramidal geometry, commonly observed for rare earth metal tris(amido) complexes such as M[N(SiMe3)2]3. Moreover, the arene anchor of the tripodal ligands is engaged in a nonnegligible interaction with the rare earth metal ions. Density functional theory calculations were performed to gain insight into the bonding interactions between the tripodal ligands and the rare earth metal ions. While LUMOs of these rare earth metal complexes are mainly π* orbitals of the arene with a minor component of metal-based orbitals, HOMO–15 and HOMO–16 of a lanthanum complex show that the arene anchor serves as a π donor to the trivalent lanthanum ion.

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Section: Introductionmentioning

confidence: 99%

Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor

et al. 2021

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“…Additional binding modes have also been discovered, and these include the facial three‐histidine (3‐His), see‐saw three‐histidine one‐carboxylate, and see‐saw four histidine binding modes [3] . Modelling of the facial 3‐His coordination has been accomplished through various nitrogen donor ligands such as 1,4,7‐triazacyclononane ( tacn ), [4] tris(2‐pyridyl)methane, [5] trispyrazolyl variants namely trispyrazolylborates, [6] trispyrazolylmethanes [7] and trisimidazolylphosphines ( TIP ) [8] . Some of these facially coordinating ligands have been used to prepare Fe‐based O 2 derived oxidants, such as superoxo and oxo species [9,10,11,12,13,14] and in catalysis [15,16] …”

Section: Figurementioning

confidence: 99%

A Facially Coordinating Tris‐Benzimidazole Ligand for Nonheme Iron Enzyme Models

et al. 2021

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Herein, we report a new tripodal tris‐benzimidazole ligand (Tbim) that structurally mimics the 3‐His coordination environment of certain nonheme mononuclear iron oxygenases. The coordination chemistry of Tbim was explored with iron(II) revealing a diverse set of coordination modes. The aerobic oxidation of biomimetic model substrate diethyl‐2‐phenylmalonate was studied using the Tbim−Fe and Fe(OTf)2.

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“…The coordination chemistry of tris(azolyl)phosphines and their oxides has been dominated for a long time by the corresponding imidazolyl derivatives, which have been used as histidine mimics in models of bioinorganic chemistry. A comprehensive review covering all these aspects has been published recently . Relatively little is known about corresponding pyrazolyl and triazolyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…A comprehensive review covering all these aspects has been published recently. 1 Relatively little is known about corresponding pyrazolyl and triazolyl derivatives. Some tris (1,2,4triazolyl)phosphine derivatives are used for triazolylation and phosphorylation reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

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The Formation of Rhenium(V) Complexes with Dihydroxyphosphoranes and Diarylphosphinic Acid Derivatives Generated from Tris(1,2,3-triazolyl)phosphine Oxides

Hagenbach

Abram

2019

Inorg. Chem.

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Tris(1-phenyl-1H-1,2,3-triazol-4-yl)phosphine oxide (OP(1,2,3Tz1‑Ph)3) and tris(1-benzyl-1H-1,2,3-triazol-4-yl)phosphine oxide (OP(1,2,3Tz1‑benz)3) react with (NBu4)[ReOCl4] under partial hydrolysis and formation of rhenium(V) complexes with unprecedented dihydroxyphosphoranato or diarylphosphinato ligands. Anionic, binuclear complexes of the compositions [Cl3(O)Re{O2P(1,2,3Tz1‑Ph)3}Re(O)Cl2]− and [Cl3(O)Re{O2P(1,2,3Tz1‑benz)3}Re(O)Cl2]− are formed as the result of a first hydrolysis step of the phosphine oxides, which has been proven by an experiment with H2 18O. Two more metal-containing products of these reactions, [ReOCl3{O2P(1,2,3Tz1‑Ph)2}]− and [Cl3(O)Re{O2P(1,2,3Tz1‑benz)2}Re(O)Cl3]−, could also be isolated and studied by X-ray diffraction. Their structures confirm a metal-mediated P–C bond cleavage and the formation of arylphosphinic acids, which finally act as ligands in the products.

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Coordination chemistry of tris(azolyl)phosphines

Cited by 12 publications

References 144 publications

Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor

Rare Earth Metal Complexes Supported by a Tripodal Tris(amido) Ligand System Featuring an Arene Anchor

A Facially Coordinating Tris‐Benzimidazole Ligand for Nonheme Iron Enzyme Models

The Formation of Rhenium(V) Complexes with Dihydroxyphosphoranes and Diarylphosphinic Acid Derivatives Generated from Tris(1,2,3-triazolyl)phosphine Oxides

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