Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects

The electronic properties and stereochemistry of mono-nuclear complexes of the copper(II) ion

Starting from the early 1990’s, the chemistry of polyvalent iodine organic compounds has experienced an explosive development. This surging interest in iodine compounds is mainly due to the very useful oxidizing properties of polyvalent organic iodine reagents, combined with their benign environmental character and commercial availability. Iodine(III) and iodine(V) derivatives are now routinely used in organic synthesis as reagents for various selective oxidative transformations of complex organic molecules. Several areas of hypervalent organoiodine chemistry have recently attracted especially active interest and research activity. These areas, in particular, include the synthetic applications of 2-iodoxybenzoic acid (IBX) and similar oxidizing reagents based on the iodine(V) derivatives, the development and synthetic use of polymer-supported and recyclable polyvalent iodine reagents, the catalytic applications of organoiodine compounds, and structural studies of complexes and supramolecular assemblies of polyvalent iodine compounds.

The chemistry of polyvalent iodine has previously been covered in four books1–4 and several comprehensive review papers.5–17 Numerous reviews on specific classes of polyvalent iodine compounds and their synthetic applications have recently been published.18–61 Most notable are the specialized reviews on [hydroxy(tosyloxy)iodo]benzene,41 the chemistry and synthetic applications of iodonium salts,29,36,38,42,43,46,47,54,55 the chemistry of iodonium ylides,56–58 the chemistry of iminoiodanes,28 hypervalent iodine fluorides,27 electrophilic perfluoroalkylations,44 perfluoroorgano hypervalent iodine compounds,61 the chemistry of benziodoxoles,24,45 polymer-supported hypervalent iodine reagents,30 hypervalent iodine-mediated ring contraction reactions,21 application of hypervalent iodine in the synthesis of heterocycles,25,40 application of hypervalent iodine in the oxidation of phenolic compounds,32,34,50–53,60 oxidation of carbonyl compounds with organohypervalent iodine reagents,37 application of hypervalent iodine in (hetero)biaryl coupling reactions,31 phosphorolytic reactivity of o-iodosylcarboxylates,33 coordination of hypervalent iodine,19 transition metal catalyzed reactions of hypervalent iodine compounds,18 radical reactions of hypervalent iodine,35,39 stereoselective reactions of hypervalent iodine electrophiles,48 catalytic applications of organoiodine compounds,20,49 and synthetic applications of pentavalent iodine reagents.22,23,26,59

The main purpose of the present review is to summarize the data that appeared in the literature following publication of our previous reviews in 1996 and 2002. In addition, a brief introductory discussion of the most important earlier works is provided in each section. The review is organized according to the classes of organic polyvalent iodine compounds with emphasis on their synthetic application. Literature coverage is through July 2008.

Chemistry of Polyvalent Iodine

Helicates as Versatile Supramolecular Complexes.

Publisher Summary This is one of two articles in this volume that is concerned with the borane-carborane structural pattern. In the other, Williams has shown how the pattern reflects the coordination number preferences of the various atoms involved. The purpose of the present article is to note some bonding implications of the pattern, and to show its relevance to a wide range of other compounds, including metal clusters, metal-hydrocarbon 7∼ complexes, and various neutral or charged hydrocarbons. Boranes and carboranes may be regarded as cluster compounds in the sense defined by Cotton; they contain a finite group or skeleton of atoms held together entirely, mainly, or at least to a significant extent by bonding directly between those atoms, even though some other atoms may be associated intimately with the cluster. Examples of their structural pattern, however, can be found far beyond the confines of what is normally regarded as cluster chemistry, so this survey includes many systems not commonly referred to as clusters.

Structural and Bonding Patterns in Cluster Chemistry

Crystal and molecular structures of dichloro[bis(diphenylphosphino)methane]palladium(II), dichloro[bis(diphenylphosphino)ethane]palladium(II), and dichloro[1,3-bis(diphenylphosphino)propane]palladium(II)

Unusual complex containing bridging vanadyl groups. Crystal structure of N,N'-propylenebis(salicylaldiminato)oxovanadium(IV)

Novel antiferromagnetic oxo-bridged manganese complex

The reactions of bismuth subcarbonate with nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA) were used to synthesize the respective bismuth complexes: (nitrilotriacetato)bismuth(III) dihydrate (1), (hydrogen ethylenediaminetetraacetato)bismuth(III) dihydrate (2), and bis(guanidinium) (diethylenetriaminepentaacetato)bismuthate(III) tetrahydrate (3). The structures of all three complexes were determined by single-crystal X-ray studies. In 1 the ligand is completely deprotonated, so that the resulting complex is neutral

Gus J. Palenik

Papers

Crystal and molecular structures of dichloro[bis(diphenylphosphino)methane]palladium(II), dichloro[bis(diphenylphosphino)ethane]palladium(II), and dichloro[1,3-bis(diphenylphosphino)propane]palladium(II)

Unusual complex containing bridging vanadyl groups. Crystal structure of N,N'-propylenebis(salicylaldiminato)oxovanadium(IV)

Novel antiferromagnetic oxo-bridged manganese complex

Syntheses and structures of bismuth(III) complexes with nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid

Bond Valence Sums in Coordination Chemistry. A Simple Method for Calculating the Oxidation State of Cobalt in Complexes Containing Only Co-O Bonds.