Reactions Of Organometallic Compounds Research Articles

ChemInform Abstract: A Novel Carbon Leaving Group in the Reaction of Organometallic Compounds with Phosphine Oxides.

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.

Evidence for new surface organotin and germanium complexes with functional groups grafted at the surface of Pt and Rh

It has been previously demonstrated that reaction of organometallic compounds with group VIII metallic surfaces can lead to grafted organometallic fragments with well defined structures. The presence of remaining alkyl groups on the catalytic surface was demonstrated by various physical and chemical techniques (EXAFS, Magnetic measurements, I.R. spectroscopy, Mössbauer, Thermoreduction, etc.). Surface organometallic complexes with an average formula M s [M′R x ] y (M=Rh, Pt, Ni; M′=Sn, Ge, Si, Se; R=Me, Et, Bu) were proposed. The impact of the presence of these alkyl groups on the selectivity and activity for various catalytic reactions is a subject of important investigations. In this work, we demonstrate that organometallic fragments with functional groups can also be grafted on a platinum or rhodium surface. We will describe the synthesis of R x M′R 4− x f (M′=Sn or Ge; R=H or Bu and R f=(CH 2) 3OH, (CH 2) 3OMe, (CH 2) 3O(CH 2) 2O(CH 2) 2OMe, or (CH 2) 4OH) and the kinetics of the reaction under atmospheric pressure of hydrogen with the silica supported platinum or rhodium catalysts. In every case, the hydrogenolysis of the organometallic complexes is not total and some organometallic fragments with functional groups remain on the surface. With R f=(CH 2) 3OH, M=Rh, M′=Sn, on average, the grafted organometallic fragment can be formulated as: Rh s [SnBu 0.4R 0.4 f] y /SiO 2. With R f=(CH 2) 3O(CH 2) 2O(CH 2) 2OMe, M=Rh, Pt, M′=Sn, on average, the grafted organometallic fragment can be formulated as: Pt s [SnBu 0.6R 0.5 f] 0.43/SiO 2 or Rh s[SnR 0.6 f] 0.6/SiO 2. With (CH 2) 3OMe, M=Rh, Pt, M′=Sn, there is formation of a grafted organometallic fragment which can be formulated on average as: Rh s [H x SnR 0.9 f] 0.9/SiO 2 and Pt s [H x SnR 1.2 f] 0.9/SiO 2. With R f=(CH 2) 4OH, M=Rh, Pt, M′=Ge, an average formula can be obtained as: Pt s [Ge(H) x R 1 f] 0.6/SiO 2, Rh s [Ge(H) x R 0.9 f] 0.6/SiO 2. Catalytic properties of these new material is under investigation.

ChemInform Abstract: Structural Aspects of Reactive Organometallic Compounds

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.

A novel carbon leaving group in the reaction of organometallic compounds with phosphine oxides

The reaction of diphenyl(methoxymethyl)phosphine oxide 1 with organometallic reagents was found to lead to substitution of the methoxymethyl group. The P-phenyl substituent showed a lower propensity to undergo a displacement.

ChemInform Abstract: The Reaction of Organometallic Compounds with the Weinreb Amide of 3,7‐Dichloroquinoline‐8‐carboxylic Acid.

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.

Chemistry of Reactive Organometallic Compounds at Low Temperatures and High Pressures: Reactions of M(CO)6(M = Cr, Mo, W), (η6-C6H3Me3)M(CO)3(M = Cr and Mo), and W(CO)5CS with H2and N2in Polyethylene Matrices

An unusual high-pressure (<5000 psi) and low-temperature (>30 K) cell is used to study the photochemistry of d6 metal carbonyl complexes and related compounds in a polyethylene (PE) matrix. This approach combines some of the advantages of traditional matrix isolation with those of low temperature solvents (e.g. liquid Xe). UV photolysis of M(CO)6 under pressures of N2 lead initially to the formation of M(CO)5N2 and, on longer photolysis, to more highly substituted M(CO)6-n(N2)n (n ≤ 4) species. Photolysis under a pressure of H2 leads to M(CO)5(η2-H2) and cis-M(CO)4(η2-H2)2, disubstituted compounds which were previously unknown for Mo and W. The thermal reactivities of all of these compounds were qualitatively established by raising the temperature of the PE matrix and monitoring the reaction with CO. The UV photolysis of W(CO)5CS and (η6-C6H3(CH3)3)M(CO)3 (M = Cr and Mo) also leads to previously uncharacterized H2 and N2 complexes. The low-temperature, high-pressure (LT−HP) cell allows gases to be exchanged during the course of a single experiment. The conditions needed for H2 and N2 to penetrate the PE and to be removed from it have been investigated, and this information has been used to study thermal exchange reactions between coordinated N2 and η2-H2 ligands in M(CO)5L compounds. It was found that the reactivity followed the order Mo > Cr > W.

The Reaction of Organometallic Compounds with the Weinreb Amide of 3,7-Dichloroquinoline-8-carboxylic Acid

The reaction of Grignard or organolithium reagents with the Weinreb amide of 3,7-dichloroquinoline-8-carboxylic acid afforded 2-substituted derivatives 5 via nucleophilic substitution reaction with hydride transfer as the major product instead of the normally expected ketone derivatives 4.

Stereoselective Synthesis of 10-Isobornyl Sulfoxides

Reaction of organometallic compounds with 10-isobornyl sulfinate 1 leads to 10-isobornyl sulfoxides with high stereoselectivity. This method has been used to prepare homochiral polydentate ligands containing the sulfinyl group.

Reaction on the addition of some organometallic compounds to 3,6-di- tert-butyl- o-benzoquinone: new o-quinones

3,6-Di- tert-butyl- o-benzosemiquinone is very convenient for the investigation of the interaction between organometallic R 2M and carbonyl compounds. The reaction of organometallic compounds R 2M with o-quinone, where R = Ph, Me, Et, Pr, 1Pr or tBu and M ≡ Zn, Cd, and Al, proceeds in two ways: (1) the single-electron oxidation of the organometallic compound by o-quinone, resulting in derivatives of alkyl(phenyl)oxyphenols; (2) the polar 1,2 and 1,4 addition of organometallic molecules to o-quinone as to conjugated ketone, which produces hydroxycyclohexadienones after hydrolysis. The relationship between these two is defined by the nature of the organometallic compound. The products of polar addition are rearranged easily in different ways, finally resulting in new o-quinones: 3-(R)-6- tert-butyl- o-benzoquinones and 3,6-di- tert-butyl-4-(R)- o-benzoquinones where R ≡ alkyl.

Mössbauer characterization of iron and cobalt dinitrosyl derivatives of 1,1′-bis(diphenylphosphino)ferrocene

The interest in the synthesis and reactivity of organometallic compounds which have two or more different metals in the same molecule has grown in recent years, due to the new chemical properties that they can present. In this work, we report the Mossbauer characterization of dppfFe(CO)3 and two novel compounds, dppfFe(NO)2 and [dppfCo(NO)2]+[SbF6]−, where dppf =1,1′-bis(diphenylphosphino)ferrocene. The complexes were also characterized by IR and31P NMR. The Mossbauer parameters of the dppfFe(NO)2 and dppfFe(CO)3, show two iron sites in the same proportions while for [dppfCo(NO)2+[SbF6]− only one site was observed.

Radical steps in the reactions of organometallic compounds with 2-methyl-2-nitrosopropane: experimental evaluation of the validity of the nitroxyl method for investigations of homolytic reactions of organometallic compounds

Radical adducts formed in the reactions of organometallic compounds of group II-V elements and of some organochromium and organoiron compounds with 2-methyl-2-nitrosopropane and phenyl(tert-butyl)nitrone were studied by ESR. Nitroso compounds and nitrones can be used as selective spin traps for investigations of homolytic reactions involving organometallic compounds.

Structure and Reactivity of Surface Species Obtained by Interaction of Organometallic Compounds with Oxidic Surfaces: IR Studies

Abstract The adsorption and reactivity of organometallic compounds on surfaces have attracted increasing attention recently. The growing interest in this area is a reflection of the many issues. of both a fundamental and applied nature. related to it. Thus, a number of studies are motivated by the attempt to gain a further understanding of the chemical bonding between the surface of the support and the organometallic molecule. and to investigate the reactivity of the surface adduct thus formed. Many studies are also devoted to the possible exploitation of either the surface adduct or the corresponding thermal decomposition products for processes of technological interest. Tailored heterogeneous catalysts are the best example of this line of research. but metallization processes and the production of semiconductor devices and electroceramic materials are also among the industrial applications which can benefit from a better understanding of the structure and reactivity of supported organometallic precursors.

ゲルマニウム陰イオンの化学―最近の進歩―

Syntheses, structures, and some reactions of organometallic compounds having germanium-metal bond have been reviewed forcusing on advances in 1980's.

Synthesis and reactivity of η5-cyclopentadienylruthenium compounds: An organometallic chemistry experiment

Procedure permits the application of concepts regarding the reactivity of organometallic compounds and the use of IR and NMR spectral data in the characterization of the synthesized complexes.

Reactions of Organometallic Compounds with Astatine-211. Application to Protein Labeling

Reactions of Organometallic Compounds with Astatine-211. Application to Protein Labeling

Kinetics and mechanisms of CO substitution reactions of metal carbonyls

Abstract

ChemInform Abstract: Carbonylation of Organometallic Compounds with Carbon Monoxide via Transmetalation

Representative examples of the carbonylation reactions of organometallic compounds of non-transition metals with carbon monoxide via transmetallation are summarized from synthetic viewpoint. Such non-transition metals as mercury, boron, thallium, silicon, tin, lead, and tellurium are found to be useful for this purpose, whereas transition metal salts such as palladium(II), rhodium(III), and rhodium(I) are employed stoicheiometrically or catalytically for transmetallation. These combined transmetallation/carbonylation reactions constitute a good method for the preparation of carboxylic acids, their esters, lactones, and ketones regio- and stereo-selectively under mild conditions; i.e., generally with atmospheric pressure of CO and at room temperature.

ChemInform Abstract: Diastereoselectivity in Reactions of Organometallic Compounds with Tetrahydrofurfural and Its Geminal Diacetates in the Presence of HMPA.

AbstractTetrahydrofurfural (I) reagiert mit den Grignard‐Verbindungen (II) in Gegenwart von HMPA fast ausschließlich zu den erythro‐Addukten (III).

ChemInform Abstract: EVIDENCE FOR SINGLE ELECTRON TRANSFER IN THE REACTIONS OF ORGANOMETALLIC COMPOUNDS WITH 2,3,3‐TRIMETHYL‐2‐BUTYL PEROXYBENZOATE

Chemischer InformationsdienstVolume 16, Issue 43 Preparative Organic Chemistry ChemInform Abstract: EVIDENCE FOR SINGLE ELECTRON TRANSFER IN THE REACTIONS OF ORGANOMETALLIC COMPOUNDS WITH 2,3,3-TRIMETHYL-2-BUTYL PEROXYBENZOATE W. H. JUN. HENDRICKSON, W. H. JUN. HENDRICKSONSearch for more papers by this authorW. D. MACDONALD, W. D. MACDONALDSearch for more papers by this authorS. T. HOWARD, S. T. HOWARDSearch for more papers by this authorE. J. COLIGADO, E. J. COLIGADOSearch for more papers by this author W. H. JUN. HENDRICKSON, W. H. JUN. HENDRICKSONSearch for more papers by this authorW. D. MACDONALD, W. D. MACDONALDSearch for more papers by this authorS. T. HOWARD, S. T. HOWARDSearch for more papers by this authorE. J. COLIGADO, E. J. COLIGADOSearch for more papers by this author First published: October 29, 1985 https://doi.org/10.1002/chin.198543173AboutPDF 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume16, Issue43October 29, 1985 RelatedInformation

Reactive Organometallic Compounds Obtained from Metallocenes and Related Compounds and Their Synthetic Applications

AbstractProgress in the synthesis of organometallic compounds via the partial or total degradation of metallocenes and related compounds under mild reaction conditions is reviewed. These degradation reactions permit highly reactive organo‐transition metal complexes to be prepared which can in turn be used in a wide range of synthetic reactions. Examples include catalytic reactions such as the cobalt‐catalyzed hydrogenation of benzene and the manganese‐catalyzed cyclotrimerization of butadiene as well as stoichiometric syntheses of mono‐ and polynuclear transition metal complexes, some of which have novel structural features.