Related Experiment Video
Updated: Jun 17, 2026
12:30
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Thioether S-ligation in a side-on micro-eta2:eta2-peroxodicopperii complex
Ga Young Park1, Yunho Lee, Dong-Heon Lee
1Department of Chemistry, The Johns Hopkins University, 3400 N Charles Street, Baltimore, MD 21218, USA.
Chemical Communications (Cambridge, England)
|December 22, 2009
Summary
Copper(I) complexes react with oxygen to form a rare side-on peroxide bound copper(II) species. This study identifies a novel thioether ligation mode for the dioxygen molecule in copper chemistry.
Area of Science:
- Inorganic Chemistry
- Coordination Chemistry
- Bioinorganic Chemistry
Background:
- Copper complexes are vital in biological systems, often involving oxygen activation.
- Understanding copper-oxygen interactions is key to catalysis and mimicking enzyme active sites.
- Previous studies on copper-dioxygen adducts have shown various binding modes.
Purpose of the Study:
- To investigate the reaction of a copper(I) complex with molecular oxygen.
- To characterize the resulting copper-dioxygen species.
- To determine the ligation mode of the dioxygen molecule.
Main Methods:
- Synthesis of the [(ANS)Cu(I)(CH3CN)](+) complex.
- Reaction of the copper(I) complex with O2.
- Spectroscopic characterization (e.g., IR spectroscopy) of the product.
- Comparison with related copper complexes with different ligands.
Main Results:
- The copper(I) complex reacts with O2 to form a dinuclear copper(II) complex, [{(ANS)Cu(II)}2(micro-eta(2):eta(2)-O2(2-))]2+.
- Infrared spectroscopy revealed a characteristic O-O stretching frequency (nu(O-O)) at 731 cm(-1).
- The dioxygen molecule was determined to be bound in a side-on (eta(2):eta(2)) fashion, involving thioether ligation.
Conclusions:
- This work reports a rare side-on binding mode for a peroxide (O2(2-)) ligand in copper chemistry.
- The thioether sulfur atom of the ANS ligand participates in the ligation of the dioxygen molecule.
- This finding expands the known coordination chemistry of copper-dioxygen species.
Related Concept Videos
01:17Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
02:26Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
01:26Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.