Pyridinium-derived N-heterocyclic carbene complexes of platinum: synthesis, structure and ligand substitution kinetics

Journal of the American Chemical Society
Jonathan S OwenJohn E Bercaw

Abstract

A series of [(R-iso-BIPY)Pt(CH(3))L ](+)X(-) complexes [R-iso-BIPY = N-(2-pyridyl)-R-pyridine-2-ylidene; (R = 4-H, 1; 4-tert-butyl, 2; 4-dimethylamino, 3; 5-dimethylamino, 4); L = SMe(2), b; dimethyl sulfoxide (DMSO), c; carbon monoxide (CO), d; X = OTf(-) = trifluoromethanesulfonate and/or [BPh(4)](-)] were synthesized by cyclometalation of the [R-iso-BIPY-H](+)[OTF](-) salts 1a-4a ([R-iso-BIPY-H](+) = N-(2-pyridyl)-R-pyridinium) with dimethylplatinum-micro-dimethyl sulfide dimer. X-ray crystal structures for 1b, 2c-4c as well as complexes having bipyridyl and cyclometalated phenylpyridine ligands, [(bipy)Pt(CH(3))(DMSO)](+) (5c) and (C(11)H(8)N)Pt(CH(3))(DMSO) (6c), have been determined. The pyridinium-derived N-heterocyclic carbene complexes display localized C-C and C-N bonds within the pyridinium ligand that are indicative of carbene pi-acidity. The significantly shortened platinum-carbon distance, for "parent" complex 1b, together with NMR parameters and the nu(CO) values for carbonyl cations 1d-4d support a degree of Pt-C10 multiple bonding, increasing in the order 3 < 4 < 2 < 1. Degenerate DMSO exchange kinetics have been determined to establish the nature and magnitude of the trans-labilizing ability of these new N-het...Continue Reading

Citations

Jun 19, 2013·Inorganic Chemistry·Antonio ZuccaSimona Galli
Sep 22, 2005·Chemical Communications : Chem Comm·Martin Albrecht, Helen Stoeckli-Evans
Jul 26, 2008·Chemical Communications : Chem Comm·Guoyong SongXingwei Li
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Aleksandr A TukovMikhail S Nechaev
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Javier Iglesias-SigüenzaJosé M Lassaletta
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Elizabeth T J StrongNathan D Jones
Feb 4, 2010·Chemical Communications : Chem Comm·George C FortmanSteven P Nolan
Nov 6, 2010·Chemical Communications : Chem Comm·Marta Roselló-MerinoSalvador Conejero
Oct 28, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Mohsen Golbon HaghighiRichard J Puddephatt
Jul 8, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Judith P Morales-CerónJosé M Vásquez-Pérez
Jul 17, 2007·Angewandte Chemie·Marion HeckenrothMartin Albrecht
Sep 25, 2008·Angewandte Chemie·Alois FürstnerChristian W Lehmann
Apr 17, 2009·Chemistry : a European Journal·Guoyong SongHongjie Zhang
Aug 20, 2009·Magnetic Resonance in Chemistry : MRC·Leszek PazderskiEdward Szłyk
Feb 17, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Sabine K SchneiderWolfgang A Herrmann
May 30, 2012·Chemical Communications : Chem Comm·Kazuhiro HataKenichiro Itami
Mar 15, 2011·Organic & Biomolecular Chemistry·Oldamur Hollóczki, László Nyulászi
Dec 6, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Vsevolod KhlebnikovMartin Albrecht
Nov 11, 2010·Angewandte Chemie·Ralte LalrempuiaMartin Albrecht
May 21, 2013·Chemical Communications : Chem Comm·Tetsushi YoshidomiKenichiro Itami
Feb 29, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Helgard G Raubenheimer, Stephanie Cronje
Feb 13, 2021·Angewandte Chemie·Kewei SunShigeki Kawai
Jun 12, 2008·The Journal of Organic Chemistry·Oldamur Hollóczki, László Nyulászi
Feb 11, 2010·Inorganic Chemistry·Sirous JamaliMehdi Rashidi
Jun 9, 2005·Chemical Reviews·Martin Lersch, Mats Tilset
Nov 14, 2019·Inorganic Chemistry·Marzieh Dadkhah AsemanS Masoud Nabavizadeh
Feb 28, 2007·Journal of the American Chemical Society·Shu-Bin ZhaoSuning Wang
Oct 5, 2006·Journal of the American Chemical Society·Eleuterio AlvarezErnesto Carmona
Jun 6, 2008·Journal of the American Chemical Society·Yves CanacRemi Chauvin
Aug 11, 2005·Journal of the American Chemical Society·Gaurav BhallaRoy A Periana

❮ Previous
Next ❯

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.