Carbonyl Cluster Anions Research Articles

Molecular orbital study of the anionic carbonyl cluster Fe2Co(CO)9CCO- and the products of its reactions with phosphines

Molecular orbital study of the anionic carbonyl cluster Fe2Co(CO)9CCO- and the products of its reactions with phosphines

Mechanistic studies on direct ethylene glycol synthesis from carbon monoxide and hydrogen 1. Homogeneous rhodium catalyst

Mechanistic studies on direct syngas conversion to ethylene glycol by a homogeneous Rh catalyst combined with a trialkylphosphine were performed. High-pressure IR studies showed that when a bulky trialkylphosphine, such as P i Pr 3( L), was added to the Rh catalyst, it gave HRh(CO) 3 L, rather than Rh carbonyl cluster anions, whereas PPh 3 and P n Bu 3 tended to decompose under the reaction conditions, forming an inactive Rh phosphidocarbonyl cluster anion, [Rh 9P(CO) 21] 2−. Kinetic studies by means of complete-mixing flow-reaction experiments revealed that the formation of formaldehyde (FAL) from CO and H 2 was rate-determining, and a bulky trialkylphosphine accelerated both the formation and the hydrogenation of FAL. It was suggested that these acceleration effects were connected with enrichment of the mononuclear hydride species and improvement of the CO insertion abilities to the hydride and the hydroxymethyl complexes by the phosphine ligand. The studies on the catalyst concentration dependencies by means of batchwise reaction revealed the involvement of dinuclear mechanisms in the formation of FAL and the reductive elimination of the bydroxymethyl and the hydroxyacetyl complexes.

Transport of electrons and sodium ions through liquid membranes mediated by platinum clusters

Using hydroxide and ferricyanide ions as the electron donor and acceptor, respectively, electrons and sodium ions are transported through organic liquid membranes by anionic carbonyl clusters of platinum.

Carbonyl cluster derived polystyrene supported platinum for asymmetric hydrogenation of α-ketoesters

Ion-pairing of anionic carbonyl clusters with cinchona alkaloid groups on cross-linked polystyrene is a viable method for the synthesis of asymmetric catalysts for the hydrogenation of methyl pyruvate.

Synthesis and Characterization of a New Binary Deca‐Osmium Carbonyl Cluster Anion—An Intermediate in the Formation of Other High‐Nuclearity Osmium Carbonyl Clusters; Crystal and Molecular Structure of (Ph4P)2 [Os10 (CO)26

The common precursor 1 to the pyrolysis products of [Os3(CO)10(NCMe)2] (2 and 3) was isolated when the reaction was performed under less extreme conditions. The pyrolysis of 1 itself (counterion Ph4P+) at 300oC gave 2 and 3 in good yield, proving its intermediacy in the reaction. The identification of 1 is a key contribution to the understanding of cluster assembly.

Synthesis and characterization of heterometallic carbonyl cluster anions

The chemistry of rhodium carbonyl cluster anions is a guide-line for the rational synthesis of those mixed-metal clusters which contain rhodium associated with a metal of group VIII. The work presented here concerns reductions of neutral carbonylic substrata and redox condensations, performed under a carbon monoxide atmosphere which limits the nuclearity to 6–7 metal atoms and induces metal redistribution amongst the various species. The reduction degree of a species ( i.e. the ratio anionic charge/metal atoms) is a function of the reducing strength (or basicity) of the medium and can be chosen with some accuracy, while the internal Rh:M ratio may be addressed working on the solution equilibria. Several M-Rh species (M = Fe, Ru, Os, Ir, Pt) have been specifically synthesized yielding the MRh 4, and MRh 5 families of homologous compounds where rhodium prevails as the main component of the metal skeleton. As a consequence the main structural and physical properties of these species are always strictly related to those of the corresponding homometallic rhodium species. On the other hand, the presence of the M heterometal acts as a ‘fine tuner’ giving to any member of these families specific properties, such as the reactivity and the NMR chemical shifts.

Chemistry of iridium carbonyl cluster complexes. Synthesis and characterization of mixed-metal carbonyl clusters via capping reactions with HgCl2 and Au(PPh3)Cl. Crystal structures of [N(PPh3)2][Ir6(.mu.3-CO)3(CO)12(.mu.3-HgCl)].cntdot.0.5C6H12 and [NMe3(CH2Ph)][Ir6(.mu.-CO)3(CO)12[.mu.3-Au(PPh3)].cntdot.C4H8O

The new anionic carbonyl clusters [Ir 6 (CO) 15 (HgCl)] − (1) and [Ir 6 (CO) 15 [Au(PPh 3 )]] − (2) have been obtained by reaction of [Ir 6 (CO) 15 ] 2− with HgCl 2 or Au(PPh 3 )Cl in tetrahydrofuran solution. The complexes have been characterized by IR(ν CO ) and NMR studies ( 13 C, 31 P, 199 Hg) and fast atom bombardment mass spectroscopy. The molecular structures of complexes 1 and 2 have been determined by single-crystal X-ray diffraction

ChemInform Abstract: Characterization of High‐Nuclearity Platinum Carbonyl Cluster Anions by 252Cf‐Plasma Desorption Mass Spectrometry: Formation of Gas‐Phase ( Pt26(CO)x)n Monocharged Ion Oligomers (n = 1‐20) from Solid‐State ( Pt26(CO)32)2‐ Dianions.

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.

Selective generation of various rhodium carbonyl cluster anions in aminated polymers and their use as catalysts for the water-gas shift reaction and deoxygenation of various nitrogen-oxygen bonds

Selective generation of various rhodium carbonyl cluster anions in aminated polymers and their use as catalysts for the water-gas shift reaction and deoxygenation of various nitrogen-oxygen bonds

Characterization of high-nuclearity platinum carbonyl cluster anions by 252Cf-plasma desorption mass spectrometry: formation of gas-phase [Pt26(CO)x]n monocharged ion oligomers (n = 1-20) from solid-state [Pt26(CO)32]2- dianions

Characterization of high-nuclearity platinum carbonyl cluster anions by 252Cf-plasma desorption mass spectrometry: formation of gas-phase [Pt26(CO)x]n monocharged ion oligomers (n = 1-20) from solid-state [Pt26(CO)32]2- dianions

Synthesis, solid-state (X-ray) and solution (nuclear magnetic resonance) studies of the hydridocarbido carbonyl cluster anion [Re7H2C(CO)21

The protonation of [Re7H(C)(CO)21]2– with CF3SO3H in dichloromethane solution produces [Re7H2C(CO)21]– which behaves as a strong acid, being completely dissociated in basic solvents. In acetonitrile the compound loses the capping Re(CO)3 unit, giving the octahedral dianion [Re6H2C(CO)18]2–. The [NEt4]+ salt crystallizes in the monoclinic system, space group P21/c(no. 14), with a= 9.394(3), b= 15.669(3), c= 27.983(6)A, β= 90.87(3)°, and Z= 4. The structure of the anion is closely related to that of the parent compounds [Re7H(C)(CO)21]2– and [Re7C(CO)21]3–, where a carbon-centred monocapped octahedron of rhenium atoms is surrounded by 21 terminal carbonyl ligands, three for each metal. The two hydride ligands have been indirectly located on the basis of potential-energy computations as double bridging, one on an edge of the basal triangle and the other one on an inter-layer edge. The 1H n.m.r. spectra at low temperature show the presence in solution of three isomers (ratio ca. 1 : 1.5 : 10) rapidly exchanging at room temperature. The possible locations of the hydrides in these species are also discussed in the light of the variable-temperature 13C n.m.r. spectra.

Rh(CO) 2X] 2 (X = Cl, CH 3COO) species suported on highly decarbonated magnesium oxide: observation of a strong effect of chloride ion on the surface organometallic chemistry

When [Rh(CO) 2(CH 3COO)] 2 or [Rh(CO) 2Cl] 2 are chemisorbed on to the surface of a decarbonated magnesium oxide their surface organometallic chemistry depends on the nature of the anionic moiety. The presence of surface chloride ions probably modify the basic character of some sites of chemisorption through formation of acidic Mg-Cl species. As on other acidic or amphoteric oxides, selective carbonylation of the surface Rh I(CO) 2 species to give physisorbed Rh 6(CO) 16 takes place even at room temperature on the surface of chlorine-doped magnesium oxide. The same behaviour is observed when hydrated RhCl 3 is used. In the absence of surface chloride ions, the previously reported surface reaction to give surface carbonyl cluster anions is observed.

Molecular Organometallic Chemistry on Surfaces: Reactivity of Metal Carbonyls on Metal Oxides

AbstractMetal carbonyls react on metal oxide surfaces to give a wide range of structures analogous to those of known compounds. The reactions leading to formation of surface‐bound metal carbonyls are explained by known molecular organometallic chemistry and the functional group chemistry of the surfaces. The reaction classes include formation of acid‐base adducts as the oxygen of a carbonyl group donates an electron pair to a Lewis acidic center; nucleophilic attack at CO ligands by basic surface hydroxyl groups or O2⊖ ions; ion‐pair formation by deprotonation of hydrido carbonyls to give carbonylate ions; interaction of bifunctional complexes with surface acid‐base pair sites such as [Mg2⊕O2⊖]; and oxidative addition of surface hydroxyl groups to metal clusters. The reactions of surface‐bound organometallic species include redox condensation and cluster formation on basic surfaces (paralleling the reactions in basic solution) as well as oxidation of mononuclear metal complexes and oxidative fragmentation of metal clusters by reaction with surface hydroxyl groups. Most supported metal carbonyls are unstable at high temperatures, but some, including osmium carbonyl cluster anions on the basic MgO surface, are strongly stabilized in the presence of CO and are precursors of catalysts for CO hydrogenation at 550 K.

ChemInform Abstract: A Case of Solid‐State Isomerism for a Rhodium Carbonyl Cluster Anion. Synthesis, Characterization in Solution and X‐Ray Crystallographic Structures of the Salts (NMe4)3(Rh11(CO)23)·Me2CO and (NMe4)3(Rh11(CO)23)·C6H5Me.

AbstractThe two title compounds containing two isomers of the same anion are obtained by oxidation of Rh7(CO)13‐6 by FeCl3 or on reacting mixtures of smaller clusters or through a stepwise cluster growth process and by recrystallization in acetone or toluene.

ChemInform Abstract: Anionic Carbonyl Clusters as Homogeneous and Supported Catalysts in Hydrogenation and Transfer Hydrogenation Reactions

ChemInformVolume 19, Issue 8 Reviews ChemInform Abstract: Anionic Carbonyl Clusters as Homogeneous and Supported Catalysts in Hydrogenation and Transfer Hydrogenation Reactions A. BASU, A. BASU Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this authorS. BHADURI, S. BHADURI Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this authorK. R. SHARMA, K. R. SHARMA Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this author A. BASU, A. BASU Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this authorS. BHADURI, S. BHADURI Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this authorK. R. SHARMA, K. R. SHARMA Edited by Ermakov, Yu. I. ;Likholobov, V. A. ;VNU Sci. Press, Utrecht, Neth.Search for more papers by this author First published: February 23, 1988 https://doi.org/10.1002/chin.198808385Read 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. Volume19, Issue8February 23, 1988 RelatedInformation

High Deoxygenation Ability of Rh Carbonyl Clusters toward Oximes Leading to Nitrile Formation

Abstract Nitriles are selectively prepared by the reaction of aldoximes with CO and H2O in the presence of rhodium carbonyl clusters. Rh12 and Rh13 carbonyl cluster anions can be detected by IR spectroscopy.

The chemical activation of iron, ruthenium, and osmium carbonyl cluster anions using oxidative addition

(The chemical activation of iron, ruthenium, and osmium carbonyl cluster anions has been achieved by investigating their oxidative electrochemistry and then matching the observed electrochemical oxidation potential with chemical reagents, by the use of oxidative addition in the presence of the required ligand; the dianionic clusters [Fe5C(CO)14]2–, [Ru3(CO)11]2–, [Ru5C(CO)14]2–, [Ru6C(CO)16]2–, [Os5(CO)15]2–, [Os7(CO)20]2–, and [Os10C(CO)24]2– have been found to react with multi-electron donor ligands in the presence of a suitable oxidant.

Intermolecular association of cyanide substituted triruthenium carbonyl cluster anions: synthesis and crystal structure of [ppn]2[Ru6(CN)2(CO)20][ppn = bis(triphenylphosphine)iminium cation

[ppn][CN][ppn = bis(triphenylphosphine)iminium cation] reacts with Ru3(CO)12 to give a cyano triruthenium carbonyl cluster anion which subsequently loses CO and dimerizes as the hexanuclear dianion [Ru6(µ-CN)2(CO)20]2–; an X-ray structural analysis shows that the structure involves two parallel ruthenium triangles linked by two axial CN bridges.

Preparation of chemically modified electrodes by attachment of platinum carbonyl clusters, and their efficient electrocatalytic action in anodic oxidation of methanol

Chemically modified electrodes, prepared by impregnating surface-modified graphite discs and anion-exchange membranes with [Pt3(CO)6]n2–(n= 3 or 5; platinum carbonyl cluster anions) by an ion-exchange technique, provide higher specific electrocatalytic activities for the anodic oxidation of methanol than conventional platinum electrodes.

Isolation of the mixed-metal carbonyl cluster anion [RuIr 3(CO) 9(μ-CO) 3] −. Crystal structure of its bis(triphenylphosphine)iminium salt

The anion [RuIr 3(CO) 12] − has been isolated as one of the products from decomposition of [RuIr 4(CO) 15] 2− in the absence of CO, and the structure of the bis(triphenylphosphine)iminium salt has been determined by X-ray diffraction. The anion is isoelectronic and isostructural with CO 4(CO) 12 and Rh 4(CO) 12, with the Ru atom located at one vertex of the metal triangle, which bears three edge-bridging carbonyls.