Mechanistic Studies of Cyclopentadienyl Ring-Slippage: A TRIR and DFT Study via Photolysis of (η1-C5Cl5)Mn(CO)5

Justin LomontCharles Harris


Ring slip is among the most widely invoked ligand distortions in organometallic chemistry, yet very few ring slipped geometries have been directly characterized. Here we investigate the ultrafast photochemistry of (η1-C5Cl5)Mn(CO)5 to characterize the “reverse ring-slip” processes that result upon ligand dissociation from this complex in polar and nonpolar solvents. (η1- C5Cl5)Mn(CO)5 readily undergoes dicarbonyl-loss upon photoexcitation across a range of UV-excitation wavelengths, and the fac- ile ejection of a second-CO during the reverse ring-slip process is shown to occur due to a mechanism that relies on the enthalpy released during the reverse ring-slip. This mechanistic paradigm is potentially widespread in organometallic reactions involving changes in ligand hapticity, carrying implications for the expansive range of Cp-ligated organometallic complexes. Experiments in CH2Cl2 solution observe formation of a solvent-coordinated product upon coordination of CH2Cl2 to the monocarbonyl-loss spe- cies. An energetic barrier to solvent coordination is present due to the need for rearrangement of the ring geometry from a three- center M-C-Cl coordination to η1 coordination to accommodate the incoming solvent molecule. Density f...Continue Reading

Related Concepts

Trending Feeds


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.

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.

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.

Hereditary Sensory Autonomic Neuropathy

Hereditary Sensory Autonomic Neuropathies are a group of inherited neurodegenerative disorders characterized clinically by loss of sensation and autonomic dysfunction. Here is the latest research on these neuropathies.

Spatio-Temporal Regulation of DNA Repair

DNA repair is a complex process regulated by several different classes of enzymes, including ligases, endonucleases, and polymerases. This feed focuses on the spatial and temporal regulation that accompanies DNA damage signaling and repair enzymes and processes.

Glut1 Deficiency

Glut1 deficiency, an autosomal dominant, genetic metabolic disorder associated with a deficiency of GLUT1, the protein that transports glucose across the blood brain barrier, is characterized by mental and motor developmental delays and infantile seizures. Follow the latest research on Glut1 deficiency with this feed.

Separation Anxiety

Separation anxiety is a type of anxiety disorder that involves excessive distress and anxiety with separation. This may include separation from places or people to which they have a strong emotional connection with. It often affects children more than adults. Here is the latest research on separation anxiety.

KIF1A Associated Neurological Disorder

KIF1A associated neurological disorder (KAND) is a rare neurodegenerative condition caused by mutations in the KIF1A gene. KAND may present with a wide range and severity of symptoms including stiff or weak leg muscles, low muscle tone, a lack of muscle coordination and balance, and intellectual disability. Find the latest research on KAND here.

Regulation of Vocal-Motor Plasticity

Dopaminergic projections to the basal ganglia and nucleus accumbens shape the learning and plasticity of motivated behaviors across species including the regulation of vocal-motor plasticity and performance in songbirds. Discover the latest research on the regulation of vocal-motor plasticity here.