Visible light driven generation and alkyne insertion reactions of stable bis-cyclometalated Pt(iv) hydrides.

Chemical Science
Dionisio PovedaPablo González-Herrero

Abstract

Hydride complexes resulting from the oxidative addition of C-H bonds are intermediates in hydrocarbon activation and functionalization reactions. The discovery of metal systems that enable their direct formation through photoexcitation with visible light could lead to advantageous synthetic methodologies. In this study, easily accessible dimers [Pt2(μ-Cl)2(C^N)2] (C^N = cyclometalated 2-arylpyridine) are demonstrated as a very convenient source of Pt(C^N) subunits, which promote photooxidative C-H addition reactions with different 2-arylpyridines (N'^C'H) upon irradiation with blue light. The resulting [PtH(Cl)(C^N)(C'^N')] complexes are the first isolable Pt(iv) hydrides arising from a cyclometalation reaction. A transcyclometalation process involving three photochemical steps is elucidated, which occurs when the C^N ligand is a monocyclometalated 2,6-diarylpyridine, and a detailed analysis of the photoreactivity associated with the Pt(C^N) moiety is provided. Alkyne insertions into the Pt-H bond of a photogenerated Pt(iv) hydride are also reported as a demonstration of the ability of this class of compounds to undergo subsequent organometallic reactions.

References

Jun 11, 2002·Inorganic Chemistry·Jason BrooksMark E Thompson
Dec 16, 2003·Chemical Society Reviews·G Sean McGrady, Gemma Guilera
Jun 9, 2005·Chemical Reviews·Martin Lersch, Mats Tilset
Mar 29, 2014·Journal of the American Chemical Society·Yue Hu, Jack R Norton
Apr 7, 2016·Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials·Colin R GroomSuzanna C Ward
Apr 9, 2016·Journal of the American Chemical Society·Fabio Juliá, Pablo González-Herrero
May 11, 2016·Chemical Reviews·Ayan Maity, Thomas S Teets
Jun 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Fabio Juliá, Pablo González-Herrero
Jun 9, 2016·Chemical Reviews·Miguel A EsteruelasMontserrat Oliván
Jun 11, 2016·Chemical Reviews·Nathan A Romero, David A Nicewicz
Jul 7, 2016·Chemical Reviews·Robin N Perutz, Barbara Procacci
Aug 3, 2016·Chemical Reviews·Eric S WiednerAaron M Appel
Sep 7, 2016·Angewandte Chemie·Anna PintusManfred Bochmann
Oct 19, 2016·Accounts of Chemical Research·Tanmay ChatterjeeEun Jin Cho
Oct 22, 2016·Chemical Reviews·Jay A Labinger
Dec 10, 2016·Journal of the American Chemical Society·Satobhisha MukherjeeFrank Glorius
Oct 4, 2017·Chemical Science·Paul A ShawJonathan P Rourke
Jul 17, 2018·Chemical Reviews·Chang-Sheng WangJean-François Soulé
Feb 27, 2019·Chemistry : a European Journal·Ángela VivancosPablo González-Herrero
Jul 2, 2019·Journal of the American Chemical Society·Ashley M WrightKaren I Goldberg
Aug 2, 2019·Angewandte Chemie·Jompol ThongpaenOlivier Baslé
Sep 19, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Ángela VivancosPablo González-Herrero
Apr 1, 2020·Chemistry : a European Journal·Juan Carlos López-LópezPablo González-Herrero

❮ Previous
Next ❯

Citations

Jan 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alexander D Ryabov
Sep 10, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Juan-Carlos López-LópezPablo González-Herrero

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR
irradiating

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.