Thermally Stable Gold(III) Alkene and Alkyne Complexes: Synthesis, Structures, and Assessment of the trans-Influence on Gold-Ligand Bond Enthalpies

Chemistry : a European Journal
Isabelle ChambrierManfred Bochmann

Abstract

The reaction of [C^C)Au(OEt2 )2 ]+ with 1,5-cyclooctadiene or norbornadiene affords the corresponding olefin complexes [(C^C)Au(COD)]SbF6 and [(C^C)Au(NBD)]SbF6 , which are thermally stable in solution and the solid state (C^C=4,4'-di-tert-butylbiphenyl-2,2'-diyl). The crystal structures of these complexes have been determined. By contrast, dienones such as dibenzylideneacetone are O- rather than C=C-bonded. The reactions of (C^C)Au(OAcF )(L) (L=PMe3 or CNxyl) with B(C6 F5 )3 in the presence of bis(1-adamantyl)acetylene give the mixed-ligand alkyne complexes [(C^C)Au(AdC≡CAd)(L)]+ , the first complexes of their type in gold chemistry. In the presence of an excess of acetylene these compounds are thermally stable in solution and as solids. The bonding of n- and π-donor ligands to AuIII fragments and the effect of the trans influence exerted by N- and C-donors was explored with the aid of DFT calculations. Results show that the Au-L bond enthalpies trans to anionic C are 35-60 % of the enthalpies trans to N, with strong π-acceptors being particularly affected. In comparison with [Me2 Au]+ , the [(C^C)Au]+ fragment is more polar and in bond enthalpy terms resembles Me2 Pt.

References

Apr 13, 2007·Angewandte Chemie·Alois Fürstner, Paul W Davies
Dec 7, 2007·Angewandte Chemie·H V Rasika DiasCharles F Campana
Oct 17, 2009·Chemistry : a European Journal·Thomas N HooperChristopher A Russell
Jul 7, 2011·Angewandte Chemie·Rajashekharayya A SanguramathChristopher A Russell
Nov 17, 2011·Angewandte Chemie·Antonio Leyva-Pérez, Avelino Corma
Dec 21, 2011·Chemical Society Reviews·Matthias Rudolph, A Stephen K Hashmi
Jan 21, 2012·Chemical Society Reviews·Le-Ping Liu, Gerald B Hammond
Sep 29, 2012·Chemistry : a European Journal·Alexander ZhdankoMartin E Maier
Nov 28, 2012·Angewandte Chemie·Nicky SavjaniManfred Bochmann
Jan 4, 2013·Angewandte Chemie·Eirin LangsethMats Tilset
Nov 2, 2013·Chemical Communications : Chem Comm·Carla Obradors, Antonio M Echavarren
Mar 15, 2011·Journal of Organometallic Chemistry·Timothy J Brown, Ross A Widenhoefer
Jun 13, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·B DavidF Mohr
Jun 20, 2014·Journal of the American Chemical Society·Eirin LangsethMats Tilset
Jun 10, 2015·Organic & Biomolecular Chemistry·Beatrice RanieriAntonio M Echavarren
Nov 26, 2015·Science Advances·Dragoş-Adrian RoşcaManfred Bochmann
Feb 26, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·David BalcellsAinara Nova
Jun 11, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Marte Sofie Martinsen HolmsenMats Tilset
Jul 8, 2016·Chemical Society Reviews·Abdullah M Asiri, A Stephen K Hashmi
Jul 13, 2017·Journal of the American Chemical Society·M Elena de OrbeAntonio M Echavarren
Sep 12, 2017·Angewandte Chemie·Luca RocchigianiManfred Bochmann

❮ Previous
Next ❯

Citations

Sep 18, 2018·Chemical Communications : Chem Comm·Marte Sofie Martinsen HolmsenMats Tilset
Nov 7, 2019·Angewandte Chemie·Jessica RodriguezDidier Bourissou
Nov 14, 2019·Chemistry : a European Journal·Isabelle ChambrierManfred Bochmann
Apr 3, 2020·Angewandte Chemie·Tyler A BartholomeCaleb D Martin
Jul 11, 2020·Angewandte Chemie·Alexandre GenouxCristina Nevado
Feb 10, 2021·Chemical Reviews·Raquel P Herrera, M Concepción Gimeno
May 1, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Flavio SabatelliPaola Belanzoni
Mar 30, 2021·Chemistry : a European Journal·Rémi JouhannetPierre de Frémont
Jun 4, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexander AhrensA Stephen K Hashmi

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Angewandte Chemie
Nicky SavjaniManfred Bochmann
Annals of the New York Academy of Sciences
R J Tedeschi
Dalton Transactions : an International Journal of Inorganic Chemistry
Ana C AlbénizBlanca Martín-Ruiz
Dalton Transactions : an International Journal of Inorganic Chemistry
Cristina Jiménez-RodríguezPiet W N M van Leeuwen
© 2022 Meta ULC. All rights reserved