Reaction Of Transition Metal Carbonyls Research Articles

Reactions of transition-metal carbonyls with anhydrous HF

The reactions of a wide range of transition-metal carbonyls with anhydrous HF are described. In particular, Ru 3(CO) 12, Os 3(CO) 12 and Ir 4(CO) 12 give the solution stable [Ru 3(CO) 12H] +, [Ru(CO) 5H] +, [Os 3(CO) 12H] +, [Os(CO) 5H] + and [Ir 4(CO) 12H 2] 2+ respectively, which have been characterised by a combination of 1H and 13C NMR spectroscopy.

Photooxidation reactions of transition metal carbonyls in low-temperature matrices

Download options Please wait... Article information DOI https://doi.org/10.1039/CS9942300309 Article type Review Article Download Citation Chem. Soc. Rev., 1994,23, 309-317 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Photooxidation reactions of transition metal carbonyls in low-temperature matrices M. J. Almond, Chem. Soc. Rev., 1994, 23, 309 DOI: 10.1039/CS9942300309 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Matthew J. Almond

Design and Properties of New IR Liquid Cells with Free Access to the Reaction Volume: Application to Temperature-Dependent Studies of the (Photo)reactions of Some Transition Metal Carbonyls

This article describes the construction and properties of new infrared cells for low- and room-temperature studies of (photo)chemical reactions. Both cells consist of three components— viz., a reaction vessel, an IR measurement cell, and a suction unit—which are interconnected by tubes, thus forming a closed system. The main advantages of the cells are that gaseous products of (photo)reactions can be removed and reagents can be added at a later stage of the reaction or at low temperature. The free access to the reaction vessel also facilitates sampling from the IR solution for analytical purposes. These great advantages are demonstrated by a few representative (photo)reactions of transition metal carbonyls.

ChemInform Abstract: Reaction of Transition Metal Carbonyls with Soluble Polyselenides: Synthesis and Structure of ((C6H5)4P)2(Re2(Se4)2(CO)6).

ChemInformVolume 21, Issue 18 Organoelement Compounds ChemInform Abstract: Reaction of Transition Metal Carbonyls with Soluble Polyselenides: Synthesis and Structure of ((C6H5)4P)2(Re2(Se4)2(CO)6). S. C. O'NEAL, S. C. O'NEAL Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this authorW. T. PENNINGTON, W. T. PENNINGTON Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this authorJ. W. KOLIS, J. W. KOLIS Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this author S. C. O'NEAL, S. C. O'NEAL Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this authorW. T. PENNINGTON, W. T. PENNINGTON Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this authorJ. W. KOLIS, J. W. KOLIS Dep. Chem., Clemson Univ., Clemson, SC 29634, USASearch for more papers by this author First published: May 1, 1990 https://doi.org/10.1002/chin.199018250Read 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, Issue18May 1, 1990 RelatedInformation

Low temperature chemical preparation of semiconducting transition metal chalcogenide films for energy conversion and storage, lubrication and surface protection

A simple technique is presented for the production of films of transition metal disulfides such as MoS2, WS2, FeS2, or RuS2 by the reaction of transition metal carbonyls (e.g. Mo(CO)6, W(CO)6, Fe(CO)5, Ru3(CO)12) with a sulfur source (e.g. S, H2S) in an organic solvent (e.g. benzene, toluene, xylene, mesitylene (1,3,5-trimethyl-benzene)) at temperatures ranging between 80 to 165 °C. The quality of the materials and films has been investigated and some applications are discussed. They include use of the chemically prepared sulfides as photoactive materials (e.g. MoS2, WS2, FeS2), as lubricating films (MoS2), as electrodes for Li-batteries (MoS2, FeS2) and for corrosion protection (RuS2).

ESR study of the reaction of transition-metal carbonyls with 2-propanol, hexamethylphosphorotriamide, and dimethylformamide using the spin trap technique

1. Transition-metal carbonyls may participate in substitution reactions with breakage of a C-H bond. 2. In contrast to mononuclear M(CO)6 metal carbonyls (M=Cr, Mo, and W), Fe(CO)5 reacts with 2-propanol, HMPTA, and DMF to form iron radical-cations. 3. Coinitiator molecules are inserted into the coordination sphere of the metal during the reactions studied.

Dissociative electron attachment reactions of transition metal carbonyls and their apparent influence on the thermalization of electrons by CO2

Dissociative electron attachment rates are measured for the transition metal carbonyls V(CO)6, Cr(CO)6, Fe(CO)5, Ni(CO)4, Mo(CO)6, and W(CO)6. Rates are measured as a function of the pressure of CO2 added to relax epithermal electrons. Derived thermal rate constants for the formation of M(CO)−n−1 from M(CO)n are 0.6, 3.0, 2.0, 2.0, 1.3, and 1.2×10−7 cm3 molecule−1 s−1, respectively. The differences in these rate constants may be attributed to the different stabilities of the molecular anion with regard to dissociation versus autodetachment. The measured rate of thermalization of electrons by CO2 varies with the metal carbonyl used and depends on the variation of the dissociative electron capture cross section with electron energy. Each system is thus tightly coupled in that the electron energy distribution is determined not only by collisional processes involving CO2 but varies as well with the energy dependent depletion of the distribution by reactant species.

Reaction of transition metal carbonyls with heterocyclic systems. VI.The interaction of Fe 2(CO) 9 with N-benzyloxypiperidine and related compounds

N-benzyloxypiperidine exhibits an unexpected type of reactivity toward Fe 2(CO) 9. Benzaldehyde and N-formylpiperidine are formed, most probably in a concerted manner, as revealed by deuterium-labeling experiments. Several mechanistic details of this reaction have been elucidated. The nature of the reaction contrasts with that of N-propyloxy- N-methylaniline, which upon treatment with Fe 2(CO) 9 undergoes insertion of a CO group into the NO bond to generate a carbamate.

Reaction of transition metal carbonyls with heterocyclic systems: V. The reaction of Fe 2(CO) 9 with bicyclic 1,2-oxazine compounds

A study of the reactions of Fe 2(CO) 9 towards the ▪ bond has extended 9-phenyl-9-aza-8-oxabicyclo[3.2.2.]nona-6-ene (I) and 8-phenyl-9-aza-7-oxabicyclo[4.2.1]nona-2,4-diene (II). The reactions are complete after 1 h at 40–50°C. Apart from the corresponding anilino alcohols, the products lack the oxygen atom of the ▪ bond. The stereochemistry of the products is indicative of an intramolecular process. Mechanistic proposals are based on an initial oxidative insertion of iron into the ▪ bond, followed by several competing reactions.

Reaction of transition metal carbonyls with heterocyclic systems—III: S N2′-type reaction of complexed π-allyl systems

A proposition regarding the capability of a complex π-allyl system to undergo a displacement reaction was advanced (eqn 2) and examined experimentally. A unique structural feature of this system is the four rather than three C atoms which intervene between the displaced and entering groups. The experiment was carried out using lactone 1c which is internally complexed and was properly labelled with deuterium. The product of its reaction with aniline has been found to be rearranged with respect to the D label, thus substantiating an S N2′-type mechanism in a complexed π-allyl system (eqn 2). From an intramolecular comparison study of the reactivity of an allyl and complexed π-allyl system in S N2′-type displacement reactions using compound 10, it was concluded that the latter is more reactive than the former. Furthermore, the π-allyl lactone 12, in which the displaced and entering groups are separated by three C atoms, was also found to undergo a displacement reaction.

Reaction of transition metal carbonyls with heterocyclic systems—II : Diironnonarcarbonyl and 1,2-oxazines

The reactivity of the ▪ bond towards diironnonacarbonyl was investigated. 3,6-Dihydro and tetrahydro-1,2-oxazines were used as model compounds. Reduction of the ▪ bond predominates in presence of water, while under anydrous conditions a CO insertion into the ▪ bond of tetrahydro-1,2-oxazine takes place. The 3,6-dihydro-1,2-oxazine in the presence of Fe 2(CO) 9 and water, yield π-allyl-Fe-σ-lactones. Carbon dioxide and aniline are also formed in this reaction. The amino alcohol 7 is an intermediate in this and analogous reactions. The lactone 3 under Al 2O 3 catalysis reacts with primary amines to yield the corresponding lactams. Mechanistic investigation of this reaction points towards a S N2′-like mechanism inasmuch as the attack of the base occurs on the terminal carbon of the π-allyl system. The lactam 4 could be readily converted into the complex π-crotonylideneaniline iron tricarbonyl for which an intramolecular 1,4-H shift was demonstrated by a labeling experiment with deuterium.

Reactions of transition-metal carbonyls with organolithium compounds. III. Synthesis of tetracarbonyl (tertiary phosphite) oxy- and amino-carbene complexes of the group VIB metals

Compounds of the general composition M(CO) 4(P(OCH 2) 3CC 2H 5)C(OC 2H 5)R have been synthesized by the reaction of organolithium reagents with M(CO) 5P(OCH 2) 3CC 2H 5 under mild conditions, where M = Cr, Mo, W; and R = CH 3, C 6H 5. Aminolysis of these compounds at −70°C with ammonia and cyclohexylamine have led to the preparation of M(CO) 4(P(OCH 2) 3CC 2H 5)C(NHR′)R species, where M = Cr, Mo, W; R = CH 3, C 6H 5; and R′ = H, C 6H 11. Infrared and proton nuclear magnetic resonance studies have been carried out on these compounds. These carbene complexes have exclusively cis structures with respect to the metal, with the lone exception Cr(CO) 4(P(OCH 2) 3CC 2H 5)C(OC 2H 5)C 6H 5, which exists in both cis and trans isomeric forms. The significance of these stereochemical observations is discussed in terms of the steric and electronic effects involved in the nucleophilic addition reactions of the organolithium reagents with bound carbon monoxide ligands.

Reactions of transition metal carbonyls with nucleophilic reagents: reactivity and bonding

Initial investigations into the reactions of organomagnesium halide reagents with metal carbonyls indicate this reaction to be adaptable to relative rate studies of nucleophilic attack on the carbonyl carbon. New carbene type complexes as well as preliminary rate studies are presented. Force constants and integrated infrared intensities of the CO stretching vibrations in M(CO) 5L compounds suggest the carbene ligand to be bound to the metal in a manner similar to phosphines and phosphites and significantly different from purely sigma donating amine ligands. Dipole moment derivative calculations and band shape analyses of the CO vibrations in metal carbonyl carbene complexes are described.

Reactions of transition metal carbonyls with organolithium compounds. II. Prediction of nucleophilic attack at carbon and resultant stereochemistry

Reactions of transition metal carbonyls with organolithium compounds. II. Prediction of nucleophilic attack at carbon and resultant stereochemistry