Effects of the number of cyclometalated rings and ancillary ligands on the rate of MeI oxidative addition to platinum(ii)-pincer complexes

Dalton Transactions : an International Journal of Inorganic Chemistry
Peyman HamidizadehS Jafar Hoseini

Abstract

Organoplatinum(ii)-pincer complexes [Pt(C^N^C)(L)] (2a; L = PPh2Me, 2b; L = pyridine (py), 2c; L = 4-picoline (pic)) are synthesized by the reaction of [Pt(C^N^C)(DMSO)], 1, with 1 equiv. of L, where HC^N^CH = 2,6-diphenylpyridine. Complexes 2 have 5d(Pt) →π*(pincer) metal-to-ligand charge-transfer bands in the visible region, which were used to easily follow the kinetics of their reactions with MeI by using UV-vis spectroscopy. An SN2 mechanism is suggested and the proposed intermediates were supported by DFT calculations. Consistent with the proposed mechanism, the rates of the reactions at different temperatures were slower for L = PPh2Me than those for L = N-donor ligands and large negative ΔS‡ values were found for all oxidative addition reactions. The rates are almost 2 times slower for L = PPh2Me as compared to L = 4-picoline because of the steric effects and the electronic effects transmitted through the ligands. To investigate the effect of the number of cyclometalated rings on the rate of MeI oxidative addition, the kinetics of the reaction of [Pt(Ph)(ppy)(py)] (Hppy = 2-phenylpyridine) and [Pt(Ph)2(py)2] (having 1 and zero cyclometalated ring, respectively) with MeI were also studied and a correlation between the num...Continue Reading

References

Feb 19, 2002·Chemical Reviews·Louis M. Rendina, Richard J. Puddephatt
May 8, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·S Masoud NabavizadehKeyamars Eskandari
Aug 10, 2010·Chemical Communications : Chem Comm·Sarah J Pike, Paul J Lusby
Nov 23, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Simin S HosseiniLouis M Rendina
Mar 3, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas LangMir Wais Hosseini
Oct 22, 2013·Chemical Communications : Chem Comm·Dhassida SooksawatPaul J Lusby
Oct 1, 1995·Annual Review of Physical Chemistry·R G Parr, W Yang
Jun 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Úrsula BelíoAntonio Martín
Apr 18, 2015·Chemical Communications : Chem Comm·Paul A ShawJonathan P Rourke
Dec 15, 2015·Chemical Communications : Chem Comm·Fabio JuliáPablo González-Herrero
Jun 24, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Paul A ShawJonathan P Rourke
Oct 7, 2016·Nature Communications·Saravanakumar ElangovanMatthias Beller
Oct 26, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Práxedes SánchezAndrés Suárez
Oct 4, 2017·Chemical Science·Paul A ShawJonathan P Rourke
Nov 10, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Hajar MolaeeMozhgan Samandar Sangari
Jul 3, 2018·Chemistry : a European Journal·Miguel BayaAntonio Martín

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

Gaussian09

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.