First-Principles Interpretation of Ligand Electrochemical (EL(L)) Parameters. Factorization of the .sigma. and .pi. Donor and .pi. Acceptor Capabilities of Ligands

Fielder, Scott S.; Osborne, Mark C.; Lever, A. B. P.; Pietro, William J.

doi:10.1021/ja00131a022

Cited by 81 publications

(65 citation statements)

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“…The data are deconvoluted into Lever electronic parameters (LEP) for individual ligands. [28] However, whereas this data can nicely be correlated with the one of the other classes of ligands, the LEP has not been determined for many NHC ligands, probably in part because of the requirement for less common electrochemical devices. [29] One established method for measuring the electron-donor ability of ligands is the synthesis of [Ni(CO) 3 (L)].…”

Section: Electronic Character Of Nhcsmentioning

confidence: 94%

The Measure of All Rings—N‐Heterocyclic Carbenes

2010

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Quantification and variation of characteristic properties of different ligand classes is an exciting and rewarding research field. N-Heterocyclic carbenes (NHCs) are of special interest since their electron richness and structure provide a unique class of ligands and organocatalysts. Consequently, they have found widespread application as ligands in transition-metal catalysis and organometallic chemistry, and as organocatalysts in their own right. Herein we provide an overview on physicochemical data (electronics, sterics, bond strength) of NHCs that are essential for the design, application, and mechanistic understanding of NHCs in catalysis.

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Section: Electronic Character Of Nhcsmentioning

confidence: 94%

The Measure of All Rings—N‐Heterocyclic Carbenes

2010

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“…There is evidence for the effects of ligand additivity on several solution properties (especially the redox potential) of a metal ion. However, such observations in solution are limited only to metal ions having closedshell electronic configurations [mainly octahedral d 6 (Datta, 1986;Fielder, Osborne, Lever & Pietro, 1995)]. However, the BVS approach shows that ligand additivity holds in the solid state, irrespective of the electronic configuration of the central atom.…”

Section: Discussionmentioning

confidence: 99%

New Bond-Valence Sum Model

Naskar¹,

Hati²,

Datta³

1997

Acta Crystallogr B Struct Sci

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A new expression is devised empirically to accommodate zero and some negative oxidation states in the bondvalence sum approach. The method is worked out in detail for a number of homoleptic copper and nickel complexes of various coordinating atoms in several oxidation states of the metals. An implication of the expression is a linear variation between 1/req and 1/rax in octahedral MX 6 moieties, where req and tax are, respectively, the average equatorial and axial bond lengths. This is verified in Cu2+X6 chromophores for X=F, O, N and S. The usefulness of the new expression in assessing the compatibility of a coordination sphere with an oxidation state of a metal ion is demonstrated by exemplary applications to some inorganic complexes, azurin and urease. references therein; Donnay & Donnay, 1973; Brown, 1978, and references therein; O'Keeffe, 1989, and references therein; Brown, 1992, and references therein;.It has been realized from the beginning that v o. bears an inverse relation with the distance (r) between two atoms i and j -a shorter bond implies higher v,j, while a longer bond indicates lower vo.. However, the exact relation between vv and r o.is not yet known. Several empirical forms have been suggested over the years (Donnay &

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“…[86] E L is a function of the σ-and π-donor and -acceptor properties of the ligand and is independent of the metal to which the ligand is bound. [87] …”

Section: Rumentioning

confidence: 99%

Ruthenium Polypyridyl Sensitisers in Dye Solar Cells Based on Mesoporous TiO₂

2011

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At present, one of the most studied molecular device for the conversion of sunlight into electricity is the dye‐sensitised solar cell (DSSC). To date, ruthenium polypyridyl complexes have shown the highest light‐to‐energy conversion efficiencies because of their photophysical, photochemical and electrochemical properties. In addition, the overall efficiency achieved by DSSCs is strongly dependent on the interfacial charge‐transfer reactions that take place between the different components of the solar cell: the injection of electrons into the conduction band of the semiconductor by the dye, the transport of electrons through the semiconductor towards the working electrode contact, dye regeneration by the redox pair present in the electrolyte and the recombination reaction between the photoinjected electrons in the semiconductor and the oxidised species of the dye and the electrolyte. This microreview comprises: (i) the operational principles of complete functional photovoltaic devices and (ii) several synthetic methods, properties and main applications of most relevant homoleptic and heteroleptic ruthenium complexes reported in the literature.

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First-Principles Interpretation of Ligand Electrochemical (EL(L)) Parameters. Factorization of the .sigma. and .pi. Donor and .pi. Acceptor Capabilities of Ligands

Cited by 81 publications

References 0 publications

The Measure of All Rings—N‐Heterocyclic Carbenes

The Measure of All Rings—N‐Heterocyclic Carbenes

New Bond-Valence Sum Model

Ruthenium Polypyridyl Sensitisers in Dye Solar Cells Based on Mesoporous TiO₂

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First-Principles Interpretation of Ligand Electrochemical (EL(L)) Parameters. Factorization of the .sigma. and .pi. Donor and .pi. Acceptor Capabilities of Ligands

Cited by 81 publications

References 0 publications

The Measure of All Rings—N‐Heterocyclic Carbenes

The Measure of All Rings—N‐Heterocyclic Carbenes

New Bond-Valence Sum Model

Ruthenium Polypyridyl Sensitisers in Dye Solar Cells Based on Mesoporous TiO2

Contact Info

Product

Resources

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Ruthenium Polypyridyl Sensitisers in Dye Solar Cells Based on Mesoporous TiO₂