The core of the matter-arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1′-ferrocenylene)arene gold(i) complexes
TL;DR: The redox-responsive nature of the complexes can be advantageously exploited in the catalytic ring-closing isomerisation of N-(2-propyn-1-yl)benzamide, where the benzene-based 2 : 3 ligand-to-metal complex has been shown to display multiple activity states depending on the degree of (reversible) oxidation in a preliminary trial.
Abstract: Changing the aromatic core of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes has profound effects on their coordination behaviour towards gold(I). Depending on the arene (s-triazine, benzene, or trifluorobenzene), four different coordination modes can be distinguished and their preference has been rationalised using computational methods. The corresponding 1 : 1 ligand-to-metal complexes, studied by variable-temperature NMR spectroscopy, revealed fluctional behaviour in solution. Given the presence of up to three or six ferrocenylene spacers per complex, their electrochemistry was investigated. The redox-responsive nature of the complexes can be advantageously exploited in the catalytic ring-closing isomerisation of N-(2-propyn-1-yl)benzamide, where the benzene-based 2 : 3 ligand-to-metal complex has been shown to display multiple activity states depending on the degree of (reversible) oxidation in a preliminary trial.
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TL;DR: Gold(I) chloride complexes are stable, widespread precatalysts that generally require activation by halide abstraction to display useful catalytic activity as discussed by the authors, which is typically performed by chloride scavenging.
Abstract: Gold(I) chloride complexes are stable, widespread precatalysts that generally require activation by halide abstraction to display useful catalytic activity. Chloride scavenging is typically perform...
25 citations
TL;DR: A review of the recent advances made with the combination of these two iconic figures in the organometallic chemistry field, since the first gold catalyzed reaction using a ferrocene ligand reported in 1986, can be found in this article .
Abstract: More than half a century after the discovery of the ferrocene structure in 1951, it remains as a suitable building block in many research areas, including catalysis with the development of key chiral catalysts. On the other hand, gold-mediated catalysis has been raised in recent years, allowing the creation of a great variety of C−C bonds and C-heteroatom bonds. In this context, this review covers the recent advances made with the combination of these two iconic figures in the organometallic chemistry field, since the first gold catalyzed reaction using a ferrocene ligand reported in 1986. The combination of the excellent properties and versatility of this metallocene, has allowed the obtainment of a plethora of ligands for metal catalysis, although their use joined to gold catalysis is still scarcely explored.
4 citations
TL;DR: In this paper , a triferrocenyl trithiophosphite was studied by X-ray single-crystal diffraction and the conformations of a given ligand were compared.
Abstract: A triferrocenyl trithiophosphite was studied by X-ray single-crystal diffraction. Triferrocenyl trithiophosphite has nine axes of internal rotation: three P–S bonds, three C–S bonds and three Fe–cyclopentadienyl axes. Rotation around the P–S bonds results in a totally asymmetric structure with three ferrocenylthio groups exhibiting different orientations towards the phosphorus lone electron pair (LEP). A comparison of DFT calculations and X-ray diffraction data is presented, herein we show which conformations are preferred for a given ligand.
1 citations
TL;DR: In this paper, a straightforward synthesis of the tetradentate phospholane ligand 1 is reported, which can be rationalised via a geometrical analysis of the ligand.
1 citations
10 Mar 2023
TL;DR: In this article , the electrostatic interactions between mainly redox-active bi-and multi-ferrocenyl functionalized five-and six-membered anti-aromatic and aromatic heterocyclic connectivities featuring either Group 13-16 main group element building blocks or d-block transition metal fragments such as titanocene or zirconocene are discussed.
Abstract: Electrostatic interactions between mainly redox-active bi- and multi-ferrocenyl [= Fe(η 5 -C 5 H 4 )(η 5 -C 5 H 5 )] functionalized five- and six-membered anti-aromatic and aromatic heterocyclic connectivities featuring either Group 13–16 main group element building blocks or d-block transition metal fragments such as titanocene or zirconocene are discussed. Inter- and intramolecular influences on the electrostatic properties in the respective compounds are described in detail and are comparatively discussed. Inter- and intramolecular impacts on the electrostatic properties and the analysis of diverse ion-pairing capabilities of a number of different electrolytes in order to obtain information on electrostatic repulsion energies are highlighted. Current trends in this field of chemistry including molecular wires and conducting polymers are reported.
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TL;DR: The Cambridge Structural Database now contains data for more than a quarter of a million small-molecule crystal structures, and projections concerning future accession rates indicate that the CSD will contain at least 500,000 crystal structures by the year 2010.
Abstract: The Cambridge Structural Database (CSD) now contains data for more than a quarter of a million small-molecule crystal structures. The information content of the CSD, together with methods for data acquisition, processing and validation, are summarized, with particular emphasis on the chemical information added by CSD editors. Nearly 80% of new structural data arrives electronically, mostly in CIF format, and the CCDC acts as the official crystal structure data depository for 51 major journals. The CCDC now maintains both a CIF archive (more than 73000 CIFs dating from 1996), as well as the distributed binary CSD archive; the availability of data in both archives is discussed. A statistical survey of the CSD is also presented and projections concerning future accession rates indicate that the CSD will contain at least 500000 crystal structures by the year 2010.
9,865 citations
TL;DR: A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96 and shows a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking.
Abstract: A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96. The proposed radii show a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking, notably the noble gases. The proposed set of radii therefore fills most of the gaps and solves some inconsistencies in currently used covalent radii. The transition metal and lanthanide contractions as well as the differences in covalent atomic radii between low spin and high spin configurations in transition metals are illustrated by the proposed radii set.
2,948 citations
TL;DR: The analysis of more than five million interatomic "non-bonded" distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested.
Abstract: The distribution of distances from atoms of a particular element E to a probe atom X (oxygen in most cases), both bonded and intermolecular non-bonded contacts, has been analyzed. In general, the distribution is characterized by a maximum at short E⋯X distances corresponding to chemical bonds, followed by a range of unpopulated distances – the van der Waals gap – and a second maximum at longer distances – the van der Waals peak – superimposed on a random distribution function that roughly follows a d3 dependence. The analysis of more than five million interatomic “non-bonded” distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested for a set of more than three million data, all of them compared to over one million bond distances.
1,030 citations
TL;DR: A comprehensive overview of the progress in this area can be found in this paper, where the N-heterocyclic carbene-based organometallic chemistry has drawn increasing attention to this class of ancillary ligands.
763 citations
TL;DR: This Review documents recent advances in asymmetric catalysis, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
Abstract: Despite the impressive progress achieved in asymmetric catalysis during the last decade, an increasing number of new catalysts, ligands, and applications are reported every year to satisfy the need to embrace a wider range of reactions and to improve the efficiency of existing processes. Because of their availability, unique stereochemical aspects, and wide variety of coordination modes and possibilities for the fine-tuning of the steric and electronic properties, ferrocene-based ligands constitute one of the most versatile ligand architectures in the current scenario of asymmetric catalysis. Over the last few years ferrocene catalysts have been successfully applied in an amazing variety of enantioselective processes. This Review documents these recent advances, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
651 citations