Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands. The quantitative analysis of ligand effects (QALE)

Fernandez, Anthony L.; Reyes, Clementina; YingLee, Tsung; Prock, Alfred; Giering, Warren P.; Haar, Christopher M.; Nolan, Steven P.

doi:10.1039/b003494k

Cited by 21 publications

(17 citation statements)

References 57 publications

(34 reference statements)

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“…Pyrrolyldiphenylphosphine 1 was chosen for its p-acceptor properties, 13 while pyrrolidinyldiphenylphosphine 2 has powerful s-donating properties. 14 In addition, the paccepting properties of phosphites vary according to the substituents on the oxygen atoms of P(OR) 3 , and are gradually increased on going from alkylphosphites 15 3-5 to arylphosphites 6. 16 Tri(isopropyl)phosphine 7 was coordinated to complement our data on ruthenium phosphine complexes, 9 and as a steric probe for future developments of this work.…”

Section: Selection Of the Ligandsmentioning

confidence: 99%

Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

et al. 2008

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The synthesis of new ruthenium(II) terpyridine bipyridine complexes bearing a phosphorus(III) ligand is presented. The steric and electronic properties of the phosphorus ligand were varied using aminophosphines, alkyl and aryl phosphites and the bulky tri(isopropyl)phosphine. All complexes were characterized by multi-nuclear NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The electronic properties of the complexes were probed by cyclic voltammetry, absorption and luminescence spectroscopy. The complexes do not show luminescence at room temperature, whereas at 77 K in an alcoholic matrix, emission is observed in the range 600-650 nm with lifetimes of 3.5-5.5 micros, originating from 3MLCT states. The MLCT transition spans over 65 nm, which corresponds to a variation of 0.4 eV in the HOMO-LUMO gap. The oxidation potential of the ruthenium varies over a broad range of 290 mV, from +1.32 V vs. SCE with L = PiPr3 to +1.61 V vs. SCE with L = P(OPh)3. This range is unprecedented upon the variation of a single monodentate ligand coordinated by the same heteroatom in the same oxidation and charge states. This work underlines the specific capacity of phosphorus in bringing up a large variety of electronic properties by changing its substituents.

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Section: Selection Of the Ligandsmentioning

confidence: 99%

Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

et al. 2008

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“…Choosing relevant descriptors is a challenge. [16,[36][37][38] Descriptors can be determined either from the molecular structure, or the physical properties. [14] Table 1 shows some typical examples of molecular descriptors for the complex shown in Figure 4.…”

Section: Case Study: Ni-catalysed Hydrocyanationmentioning

confidence: 99%

Backbone Diversity Analysis in Catalyst Design

Maldonado¹,

Hageman²,

Migliore³

et al. 2009

Adv Synth Catal

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We present a computer-based heuristic framework for designing libraries of homogeneous catalysts. In this approach, a set of given bidentate ligand-metal complexes is disassembled into key substructures ("building blocks"). These include metal atoms, ligating groups, backbone groups, and residue groups. The computer then rearranges these building blocks into a new library of virtual catalysts. We then tackle the practical problem of choosing a diverse subset of catalysts from this library for actual synthesis and testing. This is not trivial, since catalyst diversity itself is a vague concept. Thus, we first define and quantify this diversity as the difference between key structural parameters (descriptors) of the catalysts, for the specific reaction at hand. Subsequently, we propose a method for choosing diverse sets of catalysts based on catalyst backbone selection, using weighted D-optimal design. The computer selects catalysts with different backbones, where the difference is measured as a distance in the descriptors space. We show that choosing such a D-optimal subset of backbones gives more diversity than a simple random sampling. The results are demonstrated experimentally in the nickel-catalysed hydrocyanation of 3-pentenenitrile to adiponitrile. Finally, the connection between backbone diversity and catalyst diversity, and the implications towards in silico catalysis design are discussed.

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Section: Introductionmentioning

confidence: 99%

“…For instance, the weak π-acceptor ligands are not well described with this methodology. 36 From these perspectives, it could be interesting to focus on descriptors that are able to build a bridge between experimental and theoretical approaches, i.e., that benefit from the in-depth analysis provided by theory but that can also be confronted to experimental data, which are essential. One such example is provided by Coll et al who evidenced the linear correlation existing between local ionization energies and TEP, providing thus a high-performance theoretical method for evaluating TEPs.…”

Section: ■ Introductionmentioning

confidence: 99%

Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

et al. 2020

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shown to depend on the character of the ligand. "Innocent" ligands provide the spectra the most straightforward to analyze whereas the "non-innocent" ligands (which are ionized prior to the metal center) render the analysis more difficult due to an increased number of molecular orbitals in the energy range considered. A very good linear correlation is finally found between the measured adiabatic ionization energies and the interaction energy term obtained by EDA for each of these two types of ligands which opens interesting perspective for the prediction of ligand characters.

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Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands. The quantitative analysis of ligand effects (QALE)

Cited by 21 publications

References 57 publications

Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

Broad HOMO–LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core

Backbone Diversity Analysis in Catalyst Design

Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

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