It's all about Me: methyl-induced control of coordination stereochemistry by a flexible tridentate N,C,N' ligand

Dalton Transactions : an International Journal of Inorganic Chemistry
Benson M KariukiPaul D Newman

Abstract

A chiral, tridentate, pyridyl-functionalised NHC pro-ligand, S-L(Me)-H[PF₆], has been prepared diastereoselectively via a five step synthesis starting from 1R,3S-diamino-1,2,2-trimethylcyclopentane. The S prefix refers to the stereochemistry of a methyl substituted stereogenic carbon in one of the pyridyl arms which is generated by a stereoselective BH4(-) reduction of an imine precursor. The ligand has been coordinated to Rh(I) and Ir(I) to give trigonal bipyramidal complexes of the type [M(κ(3)-N,C,N'-S-L(Me))(1,5-COD)]PF6 (M = Rh, Ir) as single diastereomers. A combination of spectroscopic and X-ray techniques confirm the stereoselective formation of the thermodynamically preferred endo,endo isomer. Similar reactions with R,S-L(Me)-H[PF₆] gave a mixture of endo,endo-[M(κ(3)-N,C,N'-S-L(Me))(1,5-COD)](+) and exo,exo-[M(κ(3)-N,C,N'-R-L(Me))(1,5-COD)](+). The absolute configuration at the metal is, therefore, solely dictated by the stereochemistry of the single methylpyridyl carbon. The observation of stereoselection extends to the square planar Ni(II) complex [Ni(δ-κ(3)-N,C,N'-S-L(Me))Cl](+) which is isolated as one (δ) of the two possible conformational isomers. DFT studies have been employed to explain the observed stereosele...Continue Reading

References

Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Nov 26, 2002·Inorganic Chemistry·Andrei N VedernikovKenneth G Caulton
Mar 15, 2003·Science·Tehshik P Yoon, Eric N Jacobsen
Apr 8, 2004·Proceedings of the National Academy of Sciences of the United States of America·Andreas Pfaltz, William J Drury
Sep 7, 2006·Journal of Computational Chemistry·Stefan Grimme
Mar 21, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Lele DuanLicheng Sun
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Feb 16, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·David PughAndreas A Danopoulos
Apr 30, 2010·Nature·Hemamala I KarunadasaJeffrey R Long
Feb 2, 2011·Organic & Biomolecular Chemistry·Jeroen Wassenaar, Joost N H Reek
Jun 21, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Paul D NewmanBenson M Kariuki
May 25, 2012·Chemical Communications : Chem Comm·Paul D NewmanBenson M Kariuki
Sep 1, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Paul D NewmanBenson M Kariuki
Jan 1, 1997·Methods in Enzymology·Zbyszek Otwinowski, Wladek Minor

❮ Previous
Next ❯

Citations

Apr 27, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Katrina CoxPaul D Newman
Jul 28, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Mathilde BouchéPaul D Newman
Oct 26, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Práxedes SánchezAndrés Suárez
Oct 11, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lewis C WilkinsPaul D Newman
Jul 22, 2018·Inorganic Chemistry·Benson M Kariuki, Paul D Newman

❮ 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.