Electrolytes and interphases in Li-ion batteries and beyond.

For economical and ecological reasons, synthetic chemists are confronted with the increasing obligation of optimizing their synthetic methods. Maximizing efficiency and minimizing costs in the production of molecules and macromolecules constitutes, therefore, one of the most exciting challenges of synthetic chemistry.1-3 The ideal synthesis should produce the desired product in 100% yield and selectivity, in a safe and environmentally acceptable process.4 It is now well recognized that organometallic homogeneous catalysis offers one of the most promising approaches for solving this basic problem.2 Indeed, many of these homogeneous processes occur in high yields and selectivities and under mild reaction conditions. Most importantly, the steric and electronic properties of these catalysts can be tuned by varying the metal center and/or the ligands, thus rendering tailor-made molecular and macromolecular structures accessible.5,6 Despite the fact that various efficient methods, based on organometallic homogeneous catalysis, have been developed over the last 30 years on the laboratory scale, the industrial use of homogeneous catalytic processes is relatively limited.7 The separation of the products from the reaction mixture, the recovery of the catalysts, and the need for organic solvents are the major disadvantages in the homogeneous catalytic process. For these reasons, many homogeneous processes are not used on an industrial scale despite their benefits. Among the various approaches to address these problems, liquidliquid biphasic catalysis (“biphasic catalysis”) has emerged as one of the most important alternatives.6-11 The concept of this system implies that the molecular catalyst is soluble in only one phase whereas the substrates/products remain in the other phase. The reaction can take place in one (or both) of the phases or at the interface. In most cases, the catalyst phase can be reused and the products/substrates are simply removed from the reaction mixture by decantation. Moreover, in these biphasic systems it is possible to extract the primary products during the reaction and thus modulate the product selectivity.12 For a detailed discussion about this and other concepts of homogeneous catalyst immobilization, the reader is referred elsewhere.6,7 These biphasic systems might combine the advantages of both homogeneous (greater catalyst efficiency and mild reaction conditions) and heterogeneous (ease of catalyst recycling and separation of the products) catalysis. The advent of water-soluble organometallic complexes, especially those based on sulfonated phosphorus-containing ligands, has enabled various biphasic catalytic reactions to be conducted on an industrial scale.13-15 However, the use of water as a * Corresponding author. Fax: ++ 55 51 3316 73 04. E-mail: dupont@iq.ufrgs.br. 3667 Chem. Rev. 2002, 102, 3667−3692

https://www.chem.ccu.edu.tw/~joyce/referance/gump/IL/Chem.%20Rev.%202002,%20102,%203667.pdf

Ionic liquid (molten salt) phase organometallic catalysis.

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

This review gives a survey on the latest most representative developments and progress concerning ionic liquids, from their fundamental properties to their applications in catalytic processes. It also highlights their emerging use for biomass treatment and transformation.

Ionic liquids and catalysis: Recent progress from knowledge to applications

The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C–C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of...

Advances in Synthetic Applications of Hypervalent Iodine Compounds

New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions

Homoleptic Metal Carbonyl Cations of the Electron‐Rich Metals: Their Generation in Superacid Media Together with Their Spectroscopic and Structural Characterization

The synthesis of the bis(carbonyl)gold(I) salt, [Au(CO) 2 ][Sb 2 F 11 ], is achieved in a of gold(III) fluorosulfate, Au(SO 3 F) 3 , in HSO 3 F to give Au(CO)SO 3 F as an intermediate, followed by solvolysis in liquid antimony(V) fluoride in the presence of carbon monoxide. The use of 13 CO or C 18 O permits the synthesis of the corresponding isotopically labeled salts. The compound is thermally stable up to 130 o C.

Bis(carbonyl)gold(I) undecafluorodiantimonate(V), [Au(CO)2][Sb2F11]: synthesis, vibrational, and carbon-13 NMR study and the molecular structure of bis(acetonitrile)gold(I) hexafluoroantimonate(V), [Au(NCCH3)2][SbF6]

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO, is obtained in high yield by the solvolysis of K[B(CF3)4] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF3 group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C6F5)3BCO, is synthesized for comparison purposes by the isolation of (C6F5)3B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF3)3BCO decomposes slowly at room temperature. In the gas phase t1/2 is found to be 45 min. In the presence of a large excess of 13CO, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (EA) of 112 kJ mol-1. Low-pressure flash thermolysis of (CF3)3BCO with subsequent isolation of the products in low-temperature matrixes, indicates a lower thermal stability of the (CF3)3B fragment, than is found for (CF3)3BCO. Towa...

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO-synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure.

Erstmals wird das Tetracyanoborat-Anion in Form seines Tetrabutylammonium-Salzes durch Umsetzung von [NBu4]BX und BX3 (X = Br, Cl) in Toluol mit KCN erhalten. Nach Aufarbeitung des Rohproduktes und Umkristallisation aus CHCl3 fallen farblose, stabchenformige Einkristalle [Bu4N][B(CN)4] an. Die Metathese mit AgNO3 ergibt das Silbersalz und aus diesem mit KBr schlieslich das Kaliumsalz. Die drei Salze werden durch Rontgenbeugung an Einkristallen (Ag[B(CN)4] P 43m, a = 5.732(1) A, V = 188.3 A3, Z = 1, R1 = 0.75%; K[B(CN)4] I41/a, a = 6.976(1), c = 14.210(3) A, V = 691.5 A3, Z = 4, R1 = 1.90%; [Bu4N][B(CN)4] Pnna, a = 17.765(3), b = 11.650(2), c = 11.454(2) A, V = 2370.5 A3, Z = 4, R1 = 6.09%) und NMR-, IR-, Raman- sowie UV-Spektroskopie charakterisiert.

Helge Willner

Papers

New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions

Homoleptic Metal Carbonyl Cations of the Electron‐Rich Metals: Their Generation in Superacid Media Together with Their Spectroscopic and Structural Characterization

Bis(carbonyl)gold(I) undecafluorodiantimonate(V), [Au(CO)2][Sb2F11]: synthesis, vibrational, and carbon-13 NMR study and the molecular structure of bis(acetonitrile)gold(I) hexafluoroantimonate(V), [Au(NCCH3)2][SbF6]

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO-synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure.

Die Tetracyanoborate M[B(CN)4], M = [Bu4N]+, Ag+, K+