Rhenium Derivatives Research Articles

ChemInform Abstract: Reactions of the Polyhydride Complex ReH7(PPh3)2 with Pyridinecarboxylic Acids, 2‐Hydroxypyridine, 2‐Hydroxy‐6‐methylpyridine, and Acetylacetone. Monohydrido Complexes of Rhenium(III) and Their Oxidation to the Corresponding Rhenium(IV) Derivatives.

AbstractThe heptahydride complex (I) reacts with various organic acids, as demonstrated for (II), to afford the diamagnetic, seven‐coordinated monohydrido rhenium(III) complexes (III), (IV) and (VI).

Reactions of the polyhydride complex ReH7(PPh3)2 with pyridinecarboxylic acids, 2-hydroxypyridine, 2-hydroxy-6-methylpyridine, and acetylacetone. Monohydrido complexes of rhenium(III) and their oxidation to the corresponding rhenium(IV) derivatives

The rhenium polyhydride complex ReH 7 (PPh 3 ) 2 reacts with various organic acids to give neutral monohydrido rhenium(III) complexes of stoichiometry ReH(L) 2 (PPh 3 ) 2 , where L represents the monoanion of pyridine-2-carboxylic acid (pic), 1-isoquinolinecarboxylic acid, pyridine-2,3-dicarboxylic acid, 2-hydroxypyridine, 2-hydroxy-6-methylpyridine, and acetylacetone (acac). These complexes display a reversible couple in their cyclic voltammograms which is associated with a one-electron oxidation to their 17-electron cations. The complexes [ReH(pic) 2 (PPh 3 ) 2 ]PF 6 , ReH(acac) 2 (PPh 3 ) 2 , and [ReH(acac) 2 (PPh 3 ) 2 ]PF 6 have been structurally characterized by X-ray crystallography

New developments in the organometallic chemistry of the group IV-VII transition metals

Abstract

Electrochemical investigation on the phosphine rhenium complexes [ReCl 3(PMe 2Ph) 3] and [ReCl 4(PMe 2Ph) 2] in an aprotic medium

The cathodic and anodic behaviour of the complexes [ReCl 3(PMe 2Ph) 3] and [ReCl 4(PMe 2Ph) 2] has been studied at platinum and mercury electrodes in acetonitrile solvent. The reduction and oxidation products have been identified and both thermodynamic and kinetic aspects of the involved electrode mechanisms have been studied. In particular, new rhenium derivatives such as [ReCl 3(PMe 2Ph) 3] +. [ReCl 4(PMe 2Ph) 2] − and [ReCl 3(PMe 2Ph) 2(MeCN)] +, have been prepared. In addition the species [ReCl 4(PMe 2Ph) 2] has been obtained in a yield higher than that obtained by conventional chemical methods. The E 1 2 values of several redox couples of rhenium complexes have been calculated and compared with the corresponding values of the technetium ones; the stability of analogous rhenium and technetium compounds has been also discussed.

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, I Metallorganische Komplexe von Mangan und Rhenium mit zwei funktionellen Zentren /Preparation and Properties of and Reactions with Organometallic Heterocycles, I Organometallic Complexes of Manganese and Rhenium with two Functional Centres

Abstract The binuclear anions Na2[(OC)4MP(O)R2]2 (2a, a′, b, b′) [M = Mn: R = CH3 (a), C6H5 (a′); M = Re: R = CH3 (b), C6H5 (b′)] can be obtained quantitatively by reduction of the phosphinic acid complexes (OC)4BrMP(OH)R2 (1a, a′, b, b′) with sodium amalgam in ether. While the manganate anions 2 a, a′ can be transformed with excess sodium into the mononuclear salts Na2[(OC)4MnP(O)R2] (3a, a′), with two nucleophilic centres, the corresponding anions 2 b, b′ eliminate CO to give sparingly soluble species. From 3 a, a′ and dimethylsulphate the doubly methylated compounds CH3Mn(CO)4P(OCH3)R2 (4a, a′) are obtained. The rhenium derivatives CH3Re(CO)4P(OCH3)R2 (4b, b′) are formed only in very poor yields from 2 b, b′ and dimethylsulphate under reductive conditions. The IR, 1H NMR, and mass spectra are discussed.

Studies on metal carboxylates: XI. Reactions of rhenium carbonyl with picolinic acid and of the tungsten(I) complex [W(CO) 3(pic)] n with monodentate tertiary phosphines

The reactions of the tungsten(I) complex of picolinic acid [W(CO) 3(pic)] n with certain monodentate tertiary phosphines affords a convenient route to complexes of the types W(CO) 3(PR 3) 3 and HW(CO) 2(PR 3) 2(pic). The latter hydrido complexes of tungsten(II) have been characterized by infrared and NMR spectroscopy. The reactions of Re 2(CO) 10 with picolinic acid have also been investigated and the new series of rhenium(I) derivatives of the types Re(CO) 3(L)(pic), where L = py, 4-Ph-py, PPh 3 or dppe, and Re(CO) 2(L') 2(pic), where L' = PPh 3 or 1 2 dppe, have been isolated and characterized.

ChemInform Abstract: RHENIUM AND OSMIUM THIONITROSYL COMPLEXES

AbstractDie Nitrido‐Komplexe (I) und (III) reagieren mit 0,5 Äquivalent Dischwefeldichlorid in Methylenchlorid bei Raumtemperatur zu den Thionitrosyl‐Komplexen (II) bzw. (IV).

Intramolecular metalation with methylmanganese and methylrhenium carbonyl complexes. V. Synthesis and pathways of formation of secondary metalation products derived from tetracarbonylmethyltriphenylphosphinemanganese and -rhenium derivatives

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIntramolecular metalation with methylmanganese and methylrhenium carbonyl complexes. V. Synthesis and pathways of formation of secondary metalation products derived from tetracarbonylmethyltriphenylphosphinemanganese and -rhenium derivativesR. J. McKinney and H. D. KaeszCite this: J. Am. Chem. Soc. 1975, 97, 11, 3066–3072Publication Date (Print):May 1, 1975Publication History Published online1 May 2002Published inissue 1 May 1975https://doi.org/10.1021/ja00844a024RIGHTS & PERMISSIONSArticle Views99Altmetric-Citations45LEARN 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 (858 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Investigation of the nuclear quadrupole resonance spectra of5Mn,185Re,187Re, and127I of derivatives of manganese and rhenium cyclopentadienyltricarbonyls

1. The NQR185Re,187Re,55Mn, and127I spectra of a number of derivatives of manganese and rhenium cyclopentadienyltricarbonyls were investigated. 2. The change in the quadrupole coupling constant on the metal atom is due to a greater degree to conjugation characteristics of the substituents than to induction characteristics; moreover, in rhenium derivatives this sensitivity is approximately an order of magnitude higher than in manganese derivatives. 3. The higher NQR127I frequencies in (CO)3ReC5H4I than in (CO)3MnC6H4I permit us to consider the (CO3)ReC5H4— group as a stronger electron acceptor than (CO)3MnC5H4-.

Recent studies in photoinitiated polymerization

AbstractTwo types of photoinitiating systems are considered in this paper: (i) Group VII transition metal carbonyls in the presence of fluoro‐olefins and (ii) vanadium chelates and their derivatives.(i) The photoinitiating activities of Mn2(CO)10 and Re2(CO)10 in association with CF2 :CFCl, CF2 :CHF, CF2 :CH2, or CHF:CH2 have been studied. Methyl methacrylate was the monomer and the incident wavelengths were 436 nm and 365 nm for the manganese and Re2 (CO)10 at relatively low [T]. The kinetics of photoinitiation have been investigated. With rhenium derivatives, respectively. Of the above fluoro‐olefins, only CF2 :CFCl forms a photoinitiating system with Mn2(CO)10 while all are active with Re2(CO)10.In all the active systems the rate of polymerization ω increases with increasing fluoro‐olefin (T) concentration but finally reaches a plateau value; plateau conditions are achieved with Mn2(CO)10/CF2:CFCl (the system studied in most detail) the “sharpness” of the ω ‐ [CF2:CFCl] relation increases as the incident intensity decreases and the rate of consumption of manganese carbonyl is equal to the rate of initiation over the whole range of [CF2 :CFCl]. Quantum yields of photoinitiation have been determined for the various systems; they range from unity for Re2 (CO)10/CF2:CHF to 0.35 for Re2 (CO)10/CF2:CH2.Polymers prepared with the aid of these photoinitiators carry terminal groups in which the metal is covalently attached to the polymer chain through a unit derived from the fluoro‐olefin; for example with Mn2(CO)10/CF2:CFCl the terminal groups are (CO)5MnCF2CFCl. The initiating radicals are therefore formed by addition of an activated metal carbonyl species to the fluoro‐olefin and not by halogen abstraction as in systems such as Mn2(CO)10/CCl4, Mn2(CO)10/CBr4.On the basis of these and other results a mechanism is proposed in which photolysis of manganese carbonyl in methyl methacrylate solution leads reversibly to dissimilar fragments, only one of which forms an initiating radical with the fluoro‐olefin.The activity of fluoro‐olefins in these reactions (compared to the inertness of common vinyl monomers) is attributed to their ability to form relatively strong transition metal‐carbon bonds.(ii) Chloro‐oxobis‐(2,4‐pentanedionato) vanadium (V), VO(acac)2Cl, irradiated with light of Λ = 365 nm, initiates free‐radical polymerization of methyl methacrylate with a quantum yield of 0.02. The primary act is scission from the molecule of a chlorine atom, which is the initiating species. In the presence of an electron‐donor D (e.g., dimethylsulfoxide) ionic complexes a− are formed and photoiniate with much higher quantum yields (29‐fold in the case of dimethylsulfoxide). We believe that in these systems the primary act is electron‐transfer leading to D+ and VO(acac)2; subsequent reactions of D± then generate initiating radical species.Photolysis of the chelate VO(Q), OMe, in which Q iepresents the 8‐quinolyloxo ligand, generate initiating radicals which comprise both CH, O and CH, OH. These results provide to route to photosensitive polymers with side‐chains carrying vanadium chelates which may be used to synthesize graft copolymers and polymer networks. Preliminary experiments have indicated the feasibility of these processes.

Rhenium and osmium thionitrosyl complexes

The rhenium(V) and osmium(VI) nitrido-complexes [ReNX2(PR3)2](X = Cl, L2= 2PMe2-Ph, 2AsPh3, or bipy; X = Br, L2= 2AsPh3 or bipy), react with disulphur dichloride to give the thionitrosyl complexes [ReClX(NS)(PR3)3] and [OsClX2(NS)L2] respectively, whereas an excess of disulphur dichloride with the nitrides [ReNCl2(PR3)3] gives the rhenium(III) derivatives [ReCl3(NS)(PR3)2].

Comparative study of low-frequency vibrational spectra of cyclopentadienylmanganese tricarbonyl and cyclopentadienylrhenium tricarbonyl derivatives

1. A study was made of the dependence of the frequencies of the completely symmetric metal-ring and metal-carbonyl stretching vibrations in cyclopentadienylmanganese tricarbonyl and cyclopentadienyl-rhenium tricarbonyl derivatives on the character of the substituent in the cyclopentadienyl ring. 2. The different type of frequency shifts for the manganese and rhenium derivatives is explained by the substantially greater role of dative interaction in the formation of the metal-ring bond for the cyclopentadienylmanganese tricarbonyl derivatives.

Redox behavior of rhenium halides. IV. Reactions of rhenium(III) chloride with monodentate tertiary amines. Isolation and characterization of a new class of rhenium(II) derivatives

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRedox behavior of rhenium halides. IV. Reactions of rhenium(III) chloride with monodentate tertiary amines. Isolation and characterization of a new class of rhenium(II) derivativesD. G. Tisley and R. A. WaltonCite this: Inorg. Chem. 1973, 12, 2, 373–378Publication Date (Print):February 1, 1973Publication History Published online1 May 2002Published inissue 1 February 1973https://doi.org/10.1021/ic50120a027RIGHTS & PERMISSIONSArticle Views161Altmetric-Citations38LEARN 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 (865 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: CARBOXYLATO‐KOMPLEXE VON RHENIUM(I)‐VERBINDUNGEN

AbstractBei der Umsetzung von Natriumacetat (Ia) oder ‐benzoat (Ib) mit Pentacarbonylrheniumbromid (II) entstehen die dimeren Tricarbonylrhenium‐Verbindungen (III), die mit Kohlenmonoxid zu (IV) und mit Triphenylphosphin zu (V) reagieren.

Carboxylato-Komplexe von Rhenium(I)-Verbindungen

Hitherto unknown dimeric tricarbonyl(carboxylato)rhenium compounds are obtained according to eqn. (1) by reaction of BrRe(CO) 5 with CH 3CO 2Na and C 6H 5CO 2Na. These complexes react with carbon monoxide according to eqn. (2) or triphenylphosphine according to eqn. (3) to the monomeric pentacarbonyl- or tricarbonylbis(triphenylphosphine)(carboxylato)rhenium derivatives, respectively, in which the carboxylate ligand is unidentately coordinated. Their structures and bondings are discussed on the basis of mass and IR spectra.

Organometallic compounds with metal-metal bonds. VIII. Bis- and tris-pentacarbonylmanganese and -rhenium derivatives of tin

Organometallic compounds with metal-metal bonds. VIII. Bis- and tris-pentacarbonylmanganese and -rhenium derivatives of tin