Insertion and C-C coupling processes in reactions of the unsaturated hydride [W2Cp2(H)(μ-PCy2)(CO)2] with alkynes

Dalton Transactions : an International Journal of Inorganic Chemistry
M Angeles AlvarezM Fernanda Vega

Abstract

The title compound reacted with p-tolylacetylene at room temperature to give the 32-electron σ:π-bound alkenyl complexes trans-[W2Cp2{μ-κ:η(2)-C(p-tol)CH2}(μ-PCy2)(CO)2] and trans-[W2Cp2{μ-κ:η(2)-CHCH(p-tol)}(μ-PCy2)(CO)2], with the former complex fully rearranging into the latter one after 1 h at 363 K. Both compounds exist in solution as an isomeric equilibrium mixture (rapid on the NMR timescale) involving the alternate π-coordination of the alkenyl ligand to each of the tungsten atoms. In the presence of CO or certain solvents (THF or CH2Cl2) the α-substituted alkenyl complex was transformed instead into the cis-dicarbonyl isomer cis-[W2Cp2{μ-κ:η(2)-C(p-tol)CH2}(μ-PCy2)(CO)2] (W-W = 2.7273(8) Å). In contrast, the β-substituted alkenyl complex reacted with CO to give the saturated tricarbonyl [W2Cp2{μ-κ:η(2)-CHCH(p-tol)}(μ-PCy2)(CO)3], and with excess alkyne (under moderate heating) to yield the alkyne/alkenyl complex [W2Cp2{μ-κ:η(2)-CHCH(p-tol)}(μ-PCy2){η(2)-CHC(p-tol)}(CO)], with both products also displaying a cisoid disposition of the Cp ligands. In contrast, reactions of the title hydride with tert-butylacetylene were significantly slower and led to very air-sensitive compounds, the only isolable product from these reac...Continue Reading

References

Oct 25, 2001·Journal of the American Chemical Society·S M HolmesE B Lobkovsky
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Oct 11, 2012·Chemical Communications : Chem Comm·Jennifer C GreenGerard Parkin
Jun 5, 2013·Inorganic Chemistry·M Angeles AlvarezM Fernanda Vega
Sep 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·M Angeles AlvarezM Fernanda Vega

❮ 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.