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...

Silver-Free Catalysis with Gold(I) Chloride Complexes

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. 

/pdf/ferrocenyl-gold-complexes-as-efficient-catalysts-3okc1d6b.pdf

Ferrocenyl gold complexes as efficient catalysts

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.

https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-18-157.pdf

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

Selective formation of a supramolecular coordination complex in the nanometre scale with a ferrocene-based phospholane ligand

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. 

Electron Transfer in Mixed‐Valence Ferrocenyl‐Functionalized Five‐ and Six‐Membered Heterocycles

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.

/pdf/the-core-of-the-matter-arene-substitution-determines-the-421dx09kvw.pdf

The core of the matter-arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1′-ferrocenylene)arene gold(i) complexes

Marvin Michak

Papers

The core of the matter-arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1′-ferrocenylene)arene gold(i) complexes

Ordered and disordered structural variety in supposedly simple beryllium arsenide and beryllium phosphide

The crystal chemistry of binary beryllium dipnictides – new binary structure types between Zintl polyanions and Grimm Sommerfeld compounds