Beyond the metal-metal triple bond in binuclear cyclopentadienylchromium carbonyl chemistry

Dalton Transactions : an International Journal of Inorganic Chemistry
Xiuhui ZhangHenry F Schaefer

Abstract

The cyclopentadienylchromium carbonyls Cp(2)Cr(2)(CO)(n) and Cp*(2)Cr(2)(CO)(n) (Cp = eta(5)-C(5)H(5) and Cp* = eta(5)-Me(5)C(5); n = 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. Triplet and singlet structures are found for Cp(2)Cr(2)(CO)(3), with the triplet isomer having an apparent Cr[triple bond]Cr triple bond (2.295 A by BP86) and predicted to have a lower energy than the singlet isomer having an apparent Cr[quadruple bond]Cr quadruple bond (2.191 A by BP86). Quintet, septet, and singlet structures, as well as a highly spin contaminated triplet structure, were found for the dicarbonyl Cp(2)Cr(2)(CO)(2). In all of the Cp(2)Cr(2)(CO)(n) (n = 3, 2) structures the carbonyls are asymmetric semi-bridging groups, typically with differences of 0.3-0.5 A between the shortest and longest M-C distances. Very little difference was found between the structures and energetics of the corresponding Cp and Cp* derivatives. These DFT studies suggest that the reported unstable photolytic decarbonylation product of Cp*(2)Cr(2)(CO)(4), characterized only by its infrared nu(CO) frequencies, is the singlet isomer of the tricarbonyl Cp*(2)Cr(2)(CO)(3).

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Dec 26, 2001·Chemical Reviews·S Niu, M B Hall
Aug 18, 2005·Journal of the American Chemical Society·Hongyan WangHenry F Schaefer
Feb 8, 2006·The Journal of Chemical Physics·Filipp Furche, John P Perdew
Feb 17, 2006·Physical Chemistry Chemical Physics : PCCP·José-Luis Carreón-Macedo, Jeremy N Harvey
Aug 31, 2006·Journal of the American Chemical Society·Hongyan WangHenry F Schaefer
Sep 1, 2006·Journal of Chemical Theory and Computation·Michael Bühl, Hendrik Kabrede

❮ 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.