A Highly Reactive Co(μ-O) Diamond Core Complex that Cleaves C-H Bonds.

07:00 EST 3rd December 2019 | BioPortfolio

Summary of "A Highly Reactive Co(μ-O) Diamond Core Complex that Cleaves C-H Bonds."

The selective activation of strong sp C-H bonds at mild conditions is a key step in many biological and synthetic transformations, and an unsolved challenge for synthetic chemists. In nature, soluble methane monooxygenase (sMMO) is one representative example of nonheme dinuclear iron-dependent enzymes that activate strong sp C-H bonds by a high-valent diiron(IV) intermediate . To date, synthetic model complexes of sMMO- have shown limited abilities to oxidize strong C-H bonds. In this work, we generated a high-valent Co(μ-O) complex supported by a tetradentate TPA ligand via one-electron oxidation of its Co(μ-O) precursor . Characterization of and using X-ray absorption spectroscopy and DFT calculations showed that both species possess a diamond core structure with a short Co•••Co distance of 2.78 Å. Furthermore, is an EPR active species showing an = 1/2 signal with clear hyperfine splittings originated from the coupling of the Co nuclear spin with the electronic spin. Importantly, is a highly reactive oxidant for sp C-H bonds, and an oxygenation reagent. has the highest rate constant (1.5 M s at -60 C) for oxidizing 9,10-dihydroanthracene (DHA) compared to diamond core complexes of other first-row transition metals including Mn, Fe and Cu reported previously. Specifically, is about 4-5 orders of magnitude more reactive than the diiron analogs Fe(μ-O) and Fe(μ-O) supported by TPA and related ligands. These findings shed light on future development of more reactive approaches for C-H bond activation by bio-inspired dicobalt complexes.


Journal Details

This article was published in the following journal.

Name: Journal of the American Chemical Society
ISSN: 1520-5126


DeepDyve research library

PubMed Articles [11509 Associated PubMed Articles listed on BioPortfolio]

Synthesis of Heterocyclic Core-Expanded Bis-Naphthalene Tetracarboxylic Diimides.

A highly reactive bis-naphthalene tetracarboxylic diimide (bis-NDI) intermediate, , was designed and synthesized for core-expanded NDIs. Based on this intermediate, we achieved 9- and 11-membered core...

Superconducting boron doped nanocrystalline diamond on boron nitride ceramics.

In this work we have demonstrated the growth of nanocrystalline diamond on boron nitride ceramic. We measured the zeta potential of the ceramics to select the diamond seeds. Diamond was then grown on ...

Continuously tunable diamond Raman laser for resonance laser ionization.

We demonstrate a highly efficient, tunable, ∼5  GHz linewidth diamond Raman laser operating at 479 nm. The diamond laser was pumped by a wavelength-tunable intracavity frequency-doubled titaniu...

Nickel Phosphinidene Molecular Clusters from Organocyclophosphine Precursors.

We report a new family of nickel phosphinidene molecular clusters synthesized from the reaction of bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)2) with organocyclophosphine and trialkylphosphine. We find ...

Bifurcated Hydrogen-Bond-Stabilized Boron Analogues of Carboxylic Acids.

The reactivity of a bulky -terphenylboronic acid, DmpB(OH) [; Dmp = 2,6-bis(2,4,6-trimethylphenyl)phenyl], toward three different N-heterocyclic carbenes has been examined. The reaction of with 1 equ...

Clinical Trials [3166 Associated Clinical Trials listed on BioPortfolio]

A Single-Arm Prospective, Multi-Centered Study to Assess the SHERLOCK 3CG™ Diamond Tip Confirmation System

This study is a single-arm, prospective, multi-center study to assess clinical performance of the SHERLOCK 3CG™ Diamond Tip Confirmation System (TCS) with MODUS II software for confirming ...

Comparison Between Non-invasive Heat-flux and Invasive Core Temperature Monitoring

The body core temperature drops during general anesthesia. To maintain homeostasis, patients require warming measures. Different methods to measure body core temperature exist, which are e...

Diamond Blackfan Anemia Registry (DBAR)

The purpose of this study is to maintain a comprehensive registry of patients with the rare inherited bone marrow failure syndrome Diamond Blackfan anemia (DBA).

Burs Versus Curettes in Root Planing.

This study compares the efficacy of diamond burs and Gracey curettes in non-surgical periodontal treatment of chronic periodontitis by clinical, microbiological, biochemical parameters and...

A Pilot, Phase I/II Study of the Amino Acid Leucine in the Treatment of Patients With Transfusion-Dependent Diamond Blackfan Anemia

This study will determine the safety and possibility of giving the amino acid, leucine, in patients with Diamond Blackfan anemia(DBA)who are on dependent on red blood cell transfusions. ...

Medical and Biotech [MESH] Definitions

A complex of proteins that assemble the SNRNP CORE PROTEINS into a core structure that surrounds a highly conserved RNA sequence found in SMALL NUCLEAR RNA. They are found localized in the GEMINI OF COILED BODIES and in the CYTOPLASM. The SMN complex is named after the Survival of Motor Neuron Complex Protein 1, which is a critical component of the complex.

Diamond. A crystalline form of carbon that occurs as hard, colorless or tinted isomeric crystals. It is used as a precious stone, for cutting glass, and as bearings for delicate mechanisms. (From Grant & Hackh's Chemical Dictionary, 5th ed)

A transcription factor that dimerizes with the cofactor CORE BINDING FACTOR BETA SUBUNIT to form core binding factor. It contains a highly conserved DNA-binding domain known as the runt domain. Runx1 is frequently mutated in human LEUKEMIAS.

A transcription factor that dimerizes with CORE BINDING FACTOR BETA SUBUNIT to form core binding factor. It contains a highly conserved DNA-binding domain known as the runt domain and is involved in genetic regulation of skeletal development and CELL DIFFERENTIATION.

A 77-kDa subcomponent of complement C1, encoded by gene C1S, is a SERINE PROTEASE existing as a proenzyme (homodimer) in the intact complement C1 complex. Upon the binding of COMPLEMENT C1Q to antibodies, the activated COMPLEMENT C1R cleaves C1s into two chains, A (heavy) and B (light, the serine protease), linked by disulfide bonds yielding the active C1s. The activated C1s, in turn, cleaves COMPLEMENT C2 and COMPLEMENT C4 to form C4b2a (CLASSICAL C3 CONVERTASE).

Quick Search

DeepDyve research library

Relevant Topics

Biological Therapy
Biological therapy involves the use of living organisms, substances derived from living organisms, or laboratory-produced versions of such substances to treat disease. Some biological therapies for cancer use vaccines or bacteria to stimulate the body&rs...

Radiology is the branch of medicine that studies imaging of the body; X-ray (basic, angiography, barium swallows), ultrasound, MRI, CT and PET. These imaging techniques can be used to diagnose, but also to treat a range of conditions, by allowing visuali...

Searches Linking to this Article