Manganese Tricarbonyl Complexes Research Articles

Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen: IV. [4 + 5]-Cycloaddition konjugierter Diene an Tricarbonyl-η 5-2,4-pentadienyl-mangan

Tricarbony-η 5-2,4-pentadienyl-manganese ( 1) reacts photochemically with the conjugated dienes 1,3-butadiene ( A), 2-methyl-1,3-butadiene ( 3), Z-1,3-pentadiene ( C), E-1,3-pentadiene ( D), E,E-2,4-hexadiene ( E), 2,4-hexadien-1-ol ( F), and 2,4-hexadienoic acid methyl ester ( G) in a format [4+5] cycloaddition to tricarbonyl manganese complexes with correspondingly substituted η 3:2-2,6-cyclononadiene-1l-yl ligands ( 2A–2G). The reaction 1 and A also yields tetracarbonyl-η 3- Z,E,Z-3,6,8-nontriene-2-yl-manganese ( 3A) as by-product. No cycloaddition is observed when 1 and cyclohexadiene ( H) are irradiated. The reaction yields tetracarbonyl-η 3- E-5-(4-penten-1,3-diyl)-1,3-cyclohexadiene-manganese ( 3H), dicarbonyl-η 4:3- Z,Z-5-(3-penten-1,2-diyl)-1,3-cyclohexadiene-manganese ( 4H), and dicarbonyl-η 5:2- Z-6-(3-penten-1-yl)-2,4-cyclohexadien-1-yl-manganese ( 4H′). Under ambient conditions the complexes 4H and 4H′ react with CO to give 3H. The complexes 2A–4H′ were characterised by IR and 1H NMR spectroscopy.

Synthesis of a novel bidentate complex of η 5-C 5H 4CH 2CH(CH 3[formula omitted]n(CO) 2

Irradiation of the half-sandwich manganese tricarbonyl complex η 5-C 5H 4CH 2CH(CH 3)NH(CH 3)Mn(CO) 3m, which itself contained a secondary amine branch on the cyclopendatidenyl group, to give bidentate complex, η 5-C 5H 4CH 2(CH 3) NHCH 3M n(CO) 2. Deprotonation followed by allylation gave N-allylation compound, η 5-C 5H 4CH 2CH(CH 3) N(CH 3)(C 3H 5)M n(CO) 2, which was unequivocally identified by spectroscopic and X-ray diffraction studies.

Potentiality of an organometallic labelled streptavidin—biotin system in metalloimmunoassay

Biotin labelled with a cymantrene moiety (cyclopentadienyl manganese tricarbonyl complex) is described for the first time. Because this metallo-biotin retains full recognition for the specific glycoprotein avidin (or streptavidin), the labelled streptavidin-biotin system is proposed for use in a solid-phase competition-type metalloimmunoassay in which bovine serum albumin (BSA) is used as a model of applications. Atomic absorption spectrometry is utilized for the detection of the cymantrene-labelled biotin.

Photochemische Reaktionen von Übergangsmetall‐Organyl‐Komplexen mit Olefinen, 3. [4 + 5]‐Cycloaddition konjugierter Diene an Tricarbonyl(η5‐2,4‐dimethyl‐2,4‐pentadienyl)mangan

Photochemical Reactions of Transition Metal Organyl Complexes with Olefines, 31). – [4 + 5] Cycloaddition of Conjugated Dienes to Tricarbonyl(η5‐2,4‐dimethyl‐2,4‐pentadienyl)manganeseTricarbonyl(η5‐2,4‐dimethyl‐2,4‐pentadienyl)manganese [1] reacts photochemically with the acyclic conjugated dienes 1,3‐butadiene [A], 2‐methyl‐1,3‐butadiene [B], (E)‐1,3‐pentadiene (C), (E,E)‐2,4‐hexadiene (D), 2,4‐dimethyl‐1,3‐pentadiene (E), 2,4‐hexadien‐1‐ol (F), and methyl 2,4‐hexadienoate (G) in a formal [4 + 5] cycloaddition to give tricarbonylmanganese complexes with η3:2‐2,6‐cyclononadien‐1‐yl ligands (2A‐2G). In addition, the reaction of 1 with A yields thermolabile [η3:2:2‐1‐(3‐butene‐1,2‐diyl)‐1,3‐dimethyl‐2,6‐cyclononadiene]dicarbonylmanganese (3A) and E,E and E,Z isomers of [η3‐1‐(2‐butene‐1,1‐diyl)‐1,3‐dimethyl‐2,6‐cyclononadiene]tetracarbonylmanganese (4A, 4A] as byproducts. Similarly, 1 reacts with B to form tetracarbonyl[η3‐1‐(3‐methyl‐2‐butene‐1,1‐diyl)‐1,3,6‐trimethyl1‐2,6‐cyclononadiene]manganese (4B) in a side reaction. The crystal and molecular structures of tricarbonyl(η3:2‐1,3,5,5,7‐pentamethyl‐2,6‐cyclononadien‐1‐yl]manganese (2E) and of 3A are determined by X‐ray structure analyses. In each of the formally octahedral complexes unusual long manganese–carbon bonds are found for one coordinated CC double bond of the hydrocarbon ligands.

First example of a rapid reversible inter-ring .eta.5,.eta.5-haptotropic rearrangement in an anionic metal tricarbonyl complex containing a dibenzopentalene ligand

The first examples of migration of an organometallic group between two fused five-membered rings in transition-metal π-complexes have been found for anionic (9-methyl-10-benzylindeno [1,2-a]indene)manganese tricarbonyl complexes. The activation parameters of the rearrangement have been established with the aid of dynamic NMR spectroscopy

Stereoselective synthesis of arylglycine derivatives using arene–manganese tricarbonyl complexes

Arene–Mn(CO)3 cations react with the Schollkopf chiral glycine enolate equivalent (1) or (2) to give dienyl–Mn(CO)3 complexes which are converted to arylglycine methyl esters; the reaction sequence can be performed on arene–Mn(CO)3 complexes having protected amino acid substituents to give diaryl ethers having amino ester groups on both aromatic rings.

Anionic manganese tricarbonyl complexes of C7 and C8 cyclic dienes and polyenes: synthesis and reactions with electrophiles

Anionic manganese tricarbonyl complexes of C7 and C8 cyclic dienes and polyenes: synthesis and reactions with electrophiles

Syntheses of .eta.5-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on carbon monoxide substitution reactions

The synthesis and characterizations of some new eta/sup 5/-heterocyclic manganese tricarbonyl complexes are described. Kinetic studies are reported for CO substitution reactions of these nitrogen family eta/sup 5/-dimethylheterocyclic manganese tricarbonyl complexes. The results show that only the N-heterocycle compounds undergo CO substitution by phosphorus nucleophiles. These results are attributed to the greater electronegativity of N than that of C, P, or As. Both tricarbonyl(eta/sup 5/-3,4-dimethylpyrrolyl)manganese(I) and tricarbonyl(eta/sup 5/-2,5-dimethylpyrrolyl)manganese(I) substitute CO by an associative pathway in which the reaction rates are first order in concentration of metal complex and first order in concentration of entering nucleophile. The former compound also substitutes CO by a pathway that is independent of the concentration of incoming nucleophile. The second-order pathway is believed to involve a ring-slippage (eta/sup 5/ ..-->.. eta/sup 3/ ..-->.. eta/sup 5/) mechanism, whereas the first order pathway appears to involve a ligand-dissociation mechanism.

General route to anionic (.eta.4-diene)manganese tricarbonyl complexes. Reactions with electrophiles

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTGeneral route to anionic (.eta.4-diene)manganese tricarbonyl complexes. Reactions with electrophilesMaurice. Brookhart, Seok K. Noh, and Francis J. TimmersCite this: Organometallics 1987, 6, 8, 1829–1831Publication Date (Print):August 1, 1987Publication History Published online1 May 2002Published inissue 1 August 1987https://doi.org/10.1021/om00151a043RIGHTS & PERMISSIONSArticle Views94Altmetric-Citations12LEARN 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 (402 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis and characterization of manganese and rhenium tricarbonyl complexes with ( O,O,O)-donor ligands

Complexes of the type [(C 5H 5)Co{P(O)R 2} 3] −, R = OCH 3, OC 2H 5, react as tridentate oxygen ligands L − with [MBr(CO) 5], M = Mn, Re, in hexane or tetrahydrofuran to give the tricarbonyl derivatives [LM(CO) 3]. The slightly volatile yellow crystalline compounds have been characterized by elemental analysis, 1H NMR, IR and mass spectra. The low CO stretching frequencies indicate that the ligands L − are good π-donor ligands.

ChemInform Abstract: Tricarbonyl(η6‐cycloheptatriene)manganese Hexafluorophosphate: Reactions with Enolate Nucleophiles and Decomplexation of the Product Dienyl Complexes.

AbstractDie Reaktion des wie aufgezeichnet dargestellten Titelkomplexes (II) mit den verschiedenen Nucleophilen führt zu den 6‐substituierten 1‐5‐η‐Cycloheptadienyl‐ Mn‐Komplexen (IIIa‐g).

Orientation and structure of (.eta.5-cyclopentadienyl)rhenium and -manganese tricarbonyl complexes dissolved in liquid crystal solvents

Pour un solvant dans lequel le solute est parallele a l'axe du cristal liquide, les rapports des constantes de couplage dipolaire direct dependent de la temperature. Dans des solvants type phenylcyclohexyl ou le solute est perpendiculaire a l'axe du cristal liquide, l'orientation est independante de la temperature. Ces effets sont attribues a un echange entre 2 sites, parallele et perpendiculaire a l'axe du cristal liquide

Tricarbonyl(η6‐Cycloheptatriene)manganese Hexafluorophosphate: Reactions with Enolate Nucleophiles and Decomplexation of the Product Dienyl Complexes

AbstractReaction of tricarbonylcycloheptatrienemanganese hexafluorophosphate with a wide range of enolate nucleophiles derived from malonic esters, phenylsulfonylesters, β‐ketoesters and cyclohexanones proceeds cleanly to give 6‐substituted tricarbonyl(1–5‐η‐cycloheptadienyl)manganese complexes 3. It was found that demetallation with concomitant stereospecific hydroxylation, to give substituted cycloheptadienes, could be accomplished by direct treatment of the dienyl complexes with ceric ammonium nitrate in buffered wet acetone. Complexes 3a–3c gave mixtures of hydroxy esters and gamma lactones 6 and 7 in proportions which depended on the nature of the substituent present. A novel and potentially useful demetallative cyclofunctionalization was found to occur on treatment of hydroxy ester 3m with excess iodine in acetonitrile, to give the cyclic ether 10 as the only observable product.

Influence on transition-metal–arene complex formation of hydrogenation and rearrangement of polyaromatic substrates induced by aluminium trichloride. Octahydrophenanthrene complexes from tetralin: X-ray crystal structure of η5-1,2,3,4,5,6,7,8,9,-endo-nonahydro-9-exo-methylphenanthrenyl(tricarbonyl)-manganese

Formation of cationic tricarbonylmanganese complexes of tetralin or 9,10-dihydroanthracene from reactions of Mn(CO)5Br with naphthalene or anthracene in the presence of AlCl3 is attributed to action of the latter since it alone reduces the polyaromatic substrates under comparable conditions; reaction of tetralin with Mn(CO)5Br–AlCl3 affords in addition to the expected η6–octahydrophenanthrene analogue, the title neutral methyl derivative of which has been characterized by an X-ray crystal structure determination.

Barriers to rotation of the cyclopentadienyl ligand: spin-lattice relaxation time measurements and atom–atom potential calculations on cyclopentadienyl manganese and rhenium tricarbonyl and vanadium tetracarbonyl complexes

The barriers to cyclopentadienyl ring rotation in the solid phase have been measured by spin-lattice relaxation time methods for the organometallic complexes CpMn(CO)3 (7.24 kJ mol−1), CpRe(CO)3 (7.15 kJ mol−1), and CpV(CO)4 (7.07 kJ mol−1), where Cp = η5-C5H5. Nonbonded atom–atom potential calculations of the barriers in these complexes and in BzCr(CO)3 (Bz = η6-C6H6) show that the molecular conformation of the Mn and Re compounds is determined by crystal packing forces and that concerted ring motions are possible for the cyclopentadienyl complexes, but not for the benzene chromium tricarbonyl.

Ring contraction and other reactions of azidobenzene-and azidotoluene-tricarbonylmanganese cations

Azidobenzene- and azidotoluene-tricarbonylmanganese cations are reduced to the corresponding aniline and toluiden complexes not ony by lithium aluminium hydride but also by azide ion in polar solvents. Direct substitution of the azido group by methoxy occurs with sodium methoxide in methanol. Above 130°C nitrogen is lost from the azido compounds and ring contraction occurs yielding the corresponding (cyanocyclopentadienyl)tricarbonylmanganese complexes.

Kinetic and thermodynamic study of reactions of some substituted manganese(I) and manganese(II) tricarbonyl complexes using spectrophotometric and electrochemical techniques

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic and thermodynamic study of reactions of some substituted manganese(I) and manganese(II) tricarbonyl complexes using spectrophotometric and electrochemical techniquesA. M. Bond, B. S. Grabaric, and Zorana GrabaricCite this: Inorg. Chem. 1978, 17, 4, 1013–1018Publication Date (Print):April 1, 1978Publication History Published online1 May 2002Published inissue 1 April 1978https://doi.org/10.1021/ic50182a043RIGHTS & PERMISSIONSArticle Views316Altmetric-Citations28LEARN 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 (724 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: THE SYNTHESIS AND SPECTRAL FEATURES OF SOME CATIONIC MANGANESE(I) AND RHENIUM(I) TRICARBONYL COMPLEXES

Chemischer InformationsdienstVolume 8, Issue 35 Organoelement Compounds ChemInform Abstract: THE SYNTHESIS AND SPECTRAL FEATURES OF SOME CATIONIC MANGANESE(I) AND RHENIUM(I) TRICARBONYL COMPLEXES D. A. EDWARDS, D. A. EDWARDSSearch for more papers by this authorJ. MARSHALSEA, J. MARSHALSEASearch for more papers by this author D. A. EDWARDS, D. A. EDWARDSSearch for more papers by this authorJ. MARSHALSEA, J. MARSHALSEASearch for more papers by this author First published: August 30, 1977 https://doi.org/10.1002/chin.197735319Read 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue35August 30, 1977 RelatedInformation

The synthesis and spectral features of some cationic manganese(I) and rhenium(I) tricarbonyl complexes

More than twenty cationic manganese or rhenium tricarbonyl complexes of the types fac-[M(CO) 3L 3]ClO 4 (L = C 5H 5N or ethylenethiourea; L 3 = tri-2pyridylamine, diethylenetriamine or E-pyridine-2-carbaldehyde-2′-pyridylhydrazone), fac-[M(CO) 3X 2Y]ClO 4 (X 2 = 2 C 5H 5N, 2,2′-bipyridyl, di-2-pyridylamine, 2 PPh 3, Ph 2PCH 2PPh 2, Ph 2PCH 2CH 2PPh 2, Ph 2PCH 2CH 2AsPh 2, or Ph 2AsCH 2CH 2AsPh 2; Y = MeCN), or fac-[M(CO) 3XY 2]Cl04 (X = AsPh 3; Y= MeCN) have been prepared by displacement of acetonitrile groups from fac-[M(CO) 3(NCMe) 3]ClO 4. The dicarbonyl cationic complex [Mn(CO) 2(PPh 3) 2(NCMe) 2]ClO 4 has also been synthesised. The compounds have been characterised by conductivity measurements, and by infrared (4000-40 cm −) and 1H and 31P NMR spectroscopy. Trends in Cotton-Kraihanzel CO stretching parameters are discussed.

Notizen: Darstellung des Benzolmangantricarbonyl-Kations aus Methylcyclopentadienylmangantricarbonyl / Preparation of Cationic Benzene-manganese-tricarbonyl from Methylcyclopentadienyl-manganese-tricarbonyl

Exchange of the cyclopentadienyl ligand from methylcyclopentadienyl-manganese-tricarbonyl by benzene, toluene, xylene, mesitylene and other aromatics with AlBr3 as catalyst gives cationic aromatic manganesetricarbonyl complexes. The amount of AlBr3 and the addition of aqueous HBr do not only influence the yield but also the purity of the products. With this new method C6H6Mn(CO)3+ can be prepared in high yield from a relatively inexpensive starting material.