Cu(i) complex bearing a PNP-pincer-type phosphaalkene ligand with a bulky fused-ring Eind group: properties and applications to FLP-type bond activation and catalytic CO2 reduction

Dalton Transactions : an International Journal of Inorganic Chemistry
Katsuhiko TakeuchiJun-Chul Choi

Abstract

Herein, we report the synthesis of [Cu(Eind2-BPEP)][PF6] (2) (Eind2-BPEP = 2,6-bis(2-Eind-2-phosphaethenyl)pyridine, Eind = 1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl), a three-coordinated Cu(i) complex bearing a PNP-pincer-type phosphaalkene ligand with bulky fused-ring Eind groups. The Gutmann-Beckett test revealed that complex 2 is highly Lewis acidic and comparable in strength to B(C6F5)3, which is a relatively strong Lewis acid. In addition, 2 is more Lewis acidic than [Cu(Mes*2-BPEP)][PF6] (3), the analogous complex with less-bulky Mes* instead of Eind groups. DFT calculations using model compounds revealed that the higher Lewis acidity of 2 compared to 3 is not due to the electronic effects of the ligand, but due to a reduction in the LUMO energy caused by the steric effect of the bulky Eind groups. When combined with a tertiary amine, the highly Lewis acidic and bulky 2 exhibits the reactivity of a frustrated Lewis pair (FLP) and can activate hydrogen and phenylacetylene. Complexes 2 and 3 were found to catalyze the hydrogenation and hydrosilylation of CO2 in the presence of DBU under relatively mild conditions.

References

Jul 1, 1983·The Biochemical Journal·K KamiyaO Kennard
Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Jul 13, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Maria D Stephenson, Michaele J Hardie
Sep 7, 2006·Journal of Computational Chemistry·Stefan Grimme
Nov 18, 2006·Science·Gregory C WelchDouglas W Stephan
Apr 30, 2008·Inorganic Chemistry·Jarl Ivar van der VlugtAuke Meetsma
Aug 23, 2008·Chemistry : a European Journal·Christian MüllerDieter Vogt
Dec 22, 2009·Angewandte Chemie·Douglas W Stephan, Gerhard Erker
Jul 14, 2010·Inorganic Chemistry·Matthew F CainArnold L Rheingold
May 7, 2011·Chemical Communications : Chem Comm·Yumiko NakajimaFumiyuki Ozawa
Apr 20, 2013·Chemical Communications : Chem Comm·Liang ZhangZhaomin Hou
Dec 24, 2014·Accounts of Chemical Research·Douglas W Stephan
May 15, 2015·Angewandte Chemie·Douglas W Stephan, Gerhard Erker
Oct 13, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Yumiko NakajimaFumiyuki Ozawa
Jul 20, 2016·Journal of the American Chemical Society·Christopher M ZallAaron M Appel
Oct 19, 2016·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Fumiyuki Ozawa, Yumiko Nakajima
Nov 20, 2016·Angewandte Chemie·Katsuhiko TakeuchiFumiyuki Ozawa
Dec 13, 2016·Science·Douglas W Stephan

❮ Previous
Next ❯

Citations

Aug 14, 2020·Journal of the American Chemical Society·Michael RauchDavid Milstein

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

SHELXL
SHELXS
NBO6

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.

© 2021 Meta ULC. All rights reserved