Copper Organometallics Research Articles

Unwanted effects of X-rays in surface grafted copper(ii) organometallics and copper exchanged zeolites, how they manifest, and what can be done about them.

Copper(ii) containing materials are widely studied for a very diverse array of applications from biology, through catalysis, to many other materials chemistry based applications. We show that, for grafted copper compounds at the surface of silica, and for the study of the selective conversion of methane to methanol using copper ion-exchanged zeolites, the application of focused X-ray beams for spectroscopic investigations is subject to significant challenges. We demonstrate how unwanted effects due to the X-rays manifest, which can prevent the study of certain types of reactive systems, and/or lead to the derivation of results that are not at all representative of the behavior of the materials in question. With reference to identical studies conducted at a beamline that does not focus its X-rays, we then delineate how the total photon throughput and the brilliance of the applied X-rays affect the apparent behavior of copper in zeolites during the stepwise, high temperature and aerobic activation approach to the selective conversion of methane to methanol. We show that the use of increasingly brilliant X-ray sources for X-ray spectroscopy can bring with it significant caveats to obtaining valid and quantitative structure-reactivity relationships (QSARS) and kinetics for this class of material. Lastly, through a systematic study of these effects, we suggest ways to ensure that valuable allocations of X-ray beam time result in measurements that reflect the real nature of the chemistry under study and not that due to other, extraneous, factors.

CVD of copper and copper oxide thin films via the in situ reduction of copper(ii) nitrate—a route to conformal superhydrophobic coatings

The use of copper organometallics is an established route to generate thin films of copper. This paper describes the deposition of copper and copper(I) oxide films using relatively inexpensive copper nitrate solutions in a facile aerosol assisted chemical vapour deposition process. The composition of the resultant thin film was dependant on the solvent used and temperature of deposition, with evidence to suggest an in situ production of hydrogen which protects the copper films from oxidation. The metallic copper films were subsequently modified by oxidation to copper hydroxide and functionalised with a fluorinated thiol. The treated films were extremely hydrophobic with water contact angles that approached 180° and a less than 1° tilt angle, this a product of the extremely rough and low energy surface. The conformal substrate coverage achieved with this technique could be implemented for uniform metallic, semiconductor, hydrophilic or superhydrophobic coatings.

ChemInform Abstract: Preparation and Reactions of Functionalized Benzylic Organometallics of Zinc and Copper.

The reaction of zinc dust with primary or secondary benzylic halides 1 bearing various functional groups such as an ester, halide, cyano, or even a ketone group, in THF or, in the case of benzylic chlorides, in THF:DMSO (4:1), furnishes the corresponding zinc organometallics 2 in high yields. The reaction is accompanied by less than 10% of Wurtz coupling products. The benzylic copper organometallics 3, obtained after a transmetalation of 2 with the THF-soluble copper salt CuCN•2LiCl at −20 o C, react in excellent yields (70-95%) with various electrophiles such as acid chlorides, enones, aldehydes, allylic bromides, ethyl propiolate, and tributyltin chloride

ChemInform Abstract: A General Preparation of Highly Functionalized Zinc and Copper Organometallics at the α-Position to an Oxygen.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Preparation of Functionalized Zinc and Copper Organometallics Containing Sulfur Functionalities at the α- or γ-Position.

ChemInform Abstract: Preparation of Functionalized Zinc and Copper Organometallics Containing Sulfur Functionalities at the α- or γ-Position.

Direct Preparation of Copper Organometallics Bearing an Aldehyde Function via an Iodine—Copper Exchange.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Direct preparation of copper organometallics bearing an aldehyde function via an iodine–copper exchange

The iodine-copper exchange reaction allows the direct preparation of various aryl, heteroaryl and alkenyl cuprates bearing a formyl group, thus allowing a direct synthesis of polyfunctional aldehydes without the need of protecting groups or an additional oxidation step.

The Reaction of the α-Selenium Stabilized Copper Reagents ArSeCH2Cu(CN)ZnCI with Aldehydes

α-Arylseleno-substituted zinc and copper organometallics, in the presence of a Lewis acid, can react with aldehydes, ketones and enals with high chemoselectivity and regioselectivity.

The Reaction of the α-Selenium Stabilized Copper Reagents ArSeCH2Cu(CN)ZnCl with Aldehydes

α-Arylseleno-substituted zinc and copper organometallics, in the presence of a Lewis acid, can react with aldehydes, ketones and enals with high chemoselectivity and regioselectivity.

Ab Initio Study of Structures, Energetics, and Bonding in Formally High-Oxidation-State Copper Organometallics

Geometry-optimized structures, energies, and harmonic vibrational frequencies of closed-shell states of CuL+, XCuIL, and XCuIIIL fragments (L = CO, C2H4, C2H2; X = H-, F-, OH-, O2-, N3-) have been obtained at the MP2 level using valence-DZP-quality basis sets with effective core potentials. Natural population analyses have been used to interpret the nature of metal−ligand interactions. The computed data for all the Cu(I) species are along expected lines. Interestingly, the formally high-oxidation-state species also have effectively d10 configurations, with the electron deficiency localized in the ligands. As a result, the Cu−X bonds are long and, in a few cases, the ligand L dissociates during geometry optimization. In the computed minima, the Cu−L interaction energies are fairly large, primarily due to electrostatic interactions. The extent of π-back-donation is generally low in “Cu(III)” systems. However, a strong π-donor group enhances the ability of the metal to engage in dπ−pπ bonding with CO, C2H4, or C2H2, making it comparable to a typical CuIL system in all respects. The trends are virtually identical in all three lowest energy closed-shell states of the ethylene and acetylene complexes.

Preparation of α-Arylseleno-substituted Zinc and Copper Organometallics and their Application in the Synthesis of α-Arylselenomethyl Ketones

α-Arylseleno-substituted zinc and copper organometallics, prepared by zinc insertion into the carbon–chlorine bond of α-chloromethyl aryl selenides and with CuCN–2LiCl transmetallation to the corresponding copper reagents, react with acyl chlorides to give α-arylselenomethyl ketones based on the formation of a new carbon–carbon bond.

ChemInform Abstract: Preparation and Reactivity of Polyfunctional Zinc and Copper Organometallics Bearing Sulfur Functionalities.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Preparation and Reactivity of Polyfunctional Zinc and Copper Organometallics Bearing Sulfur Functionalities

Iodomethylthiobenzoate 5 and α-chloroalkyl phenyl sulfides 6 were found to insert zinc dust in THF under very mild conditions (10–25 °C, 0.5–2 h) leading to zinc α-thioorganometallics. After a transmetallation with CuCN·2 LiCl, the corresponding copper reagents 8 and 7 reacted with various electrophiles (1-haloalkynes, aldehydes, enones, acyl chlorides, allylic halides, trialkyltin halides) affording polyfunctional thioesters and sulfides of type 9 or 10 in excellent yields. Of special interest is that, contrary to lithium α-thiocarbanions, these zinc-copper reagents can bear various functional groups like esters or nitriles. The same approach allowed the preparation of various γ-thio-substituted zinc and copper reagents bearing phenylthio, phenylsulfinyl, or α-(phenylsulfonyl)vinyl functionalities ( 20–22) which also display a good ability to form new carboncarbon bonds.

ChemInform Abstract: A New Preparation of Highly Functionalized Aromatic and Heteroaromatic Zinc and Copper Organometallics.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Preparation and reactions of zinc and copper organometallics bearing acidic hydrogens

Preparation and reactions of zinc and copper organometallics bearing acidic hydrogens

Selective multiple methylene insertion reactions mediated by iodomethylzine iodide: Mechanistic considerations and synthetic applications

The reaction of alkynylcoppers 1 with an excess of iodomethylzinc iodide selectively furnishes the quadruple methylene insertion copper organometallics 2 in fair to good yields. The mechanism of the reaction has been investigated and postulated intermediates such as 4 or 8 have been trapped with electrophiles like aldehydes or ketones in excellent yields. A new in situ preparation of propargylic copper derivatives 4 starting from readily available alkynylcopper compounds has been developed leading to homopropargylic alcohols in 80–95% yield.

A general preparation of highly functionalized zinc and copper organometallics at the .alpha.-position to an oxygen [Erratum to document cited in CA113(11):97016x

A general preparation of highly functionalized zinc and copper organometallics at the .alpha.-position to an oxygen [Erratum to document cited in CA113(11):97016x

ChemInform Abstract: Direct Conversion of Vinylic Organocopper Compounds to Allylic Zinc and Copper Organometallics.

ChemInformVolume 21, Issue 48 Preparative Organic Chemistry ChemInform Abstract: Direct Conversion of Vinylic Organocopper Compounds to Allylic Zinc and Copper Organometallics. P. KNOCHEL, P. KNOCHEL Dep. Chem., Univ. Mich., Ann Arbor, MI 48109, USASearch for more papers by this authorS. A. RAO, S. A. RAO Dep. Chem., Univ. Mich., Ann Arbor, MI 48109, USASearch for more papers by this author P. KNOCHEL, P. KNOCHEL Dep. Chem., Univ. Mich., Ann Arbor, MI 48109, USASearch for more papers by this authorS. A. RAO, S. A. RAO Dep. Chem., Univ. Mich., Ann Arbor, MI 48109, USASearch for more papers by this author First published: November 27, 1990 https://doi.org/10.1002/chin.199048086Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue48November 27, 1990 RelatedInformation

A general preparation of highly functionalized zinc and copper organometallics at the .alpha.-position to an oxygen

α-Bromoalkyl acetates, which are readily prepared by the addition of acetyl bromide to aldehydes, insert zinc under mild conditions affording, after the addition of CuCN.2LiCl, polyfunctional α-acetoxy copper reagents. Their reactivity toward various organic electrophiles is described

A direct conversion of vinylic organocopper compounds to allylic zinc and copper organometallics

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA direct conversion of vinylic organocopper compounds to allylic zinc and copper organometallicsPaul Knochel and S. Achyutha RaoCite this: J. Am. Chem. Soc. 1990, 112, 16, 6146–6148Publication Date (Print):August 1, 1990Publication History Published online1 May 2002Published inissue 1 August 1990https://doi.org/10.1021/ja00172a051RIGHTS & PERMISSIONSArticle Views577Altmetric-Citations55LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (385 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts