Recent developments in coordination chemistry

The discovery of 7r-allylic complexes is an exciting recent development in coordination chemistry. In these complexes the bonding of the allylic radical... 

J. C. Bailar, Jr., Hiroshi Itatani, Mary Jean Sirotek Crespi and John Geldard, Some Recent Developments in Coordination Chemistry, Advances in Chemistry Series, American Chemical Society, No. 62, p. 103 (1967). 

Uson, R. and Laguna, A. (1986) Recent Developments In Arylgold Chemistry. Coordination Chemistry Reviews, 70,... 

Carbon dioxide coordination chemistry is a very recent development in organometallic chemistry. The first claims for coordination complexes of C02 did not appear until 1969, and only recently have any number of well-characterized complexes been reported. Consequently, no sweeping generalizations can be made regarding the nature of C02 coordination complexes, but a few tentative guidelines can be inferred. 

The discovery that the nitrosyl ligand is capable of binding to transition metals in two isomeric valence forms1 is one of the most dramatic recent developments in organometallic chemistry. Since bent NO donates 2 fewer electrons to the metal than the linear isomer does, linear-bent tautomerism raises the possibility of coordinative unsaturation and catalysis.2 In fact, complexes of nitric oxide are receiving increasing attention as catalysts,3 since they are more reactive than the corresponding carbonyls.4... 

Abstract Recent developments in the chemistry of phosphinines are reported. This chapter presents and discusses the most important breakthroughs achieved during the last decade. New synthetic approaches allowing the synthesis of polyfunctional phosphinines as well as improvements of well known methods are reported. The use of phosphinines in coordination chemistry is also presented with particular emphasis on their use in the stabilization of low valent and highly reduced transition metal complexes. Another aim of this review is to discuss recent applications of phosphinines, and structures derived directly from phosphinines such as phosphacyclohexadienyl anions and phosphabarrelenes, as ligands in homogeneous catalysis. 

The first chapter in the second volume of this series deals with the physical properties of a novel group of melts, the organic molten salts as applied to the testing of models of molten salt behavior. In addition, there are three chapters on the chemistry of solute species in melts. One of these chapters deals with solubilities of reactive gases in melts. Another chapter treats coordination chemistry and electronic spectroscopy of Group VIII elements in fused salts. The last chapter is concerned with recent developments in electroanalytical chemistry in molten salt systems. 

Developments in NHC chemistry have been considerable, and an exponential increase in pubhcations has occurred since the mid 1990s. Numerous reviews have appeared providing comprehensive experimental and theoretical desaiptions of advances in the field [1-13], and very recently a volume of Coordination Chemistry Reviews and complete issues of Dalton Transactions and European Journal of Inorganic Chemistry have been dedicated to NHC chanistry [14], An excellent review on the topic of catalyst decomposition was pubhshed in 2004 [7], and consequently the present chapter will... 

Recent developments in the coordination chemistry of selenoether and telluroether ligands6... 

One of the more important recent developments in organometallic aluminum chemistry has been the formation and isolation of low-coordinate compounds, and, in particular, cations. These were first prepared in reactions of various aluminum reagents with crown ethers to form the inclusion compounds known as liquid clathrates. 71,72 Most of the evidence supports the presence of ion pairs as the basis of the solvent inclusion effect. Indeed, the compound [AlMe2-18-crown-6]+[AlMe2Cl2] was isolated from one such system (the cation is shown in Figure 6(a)).73 This was the first time the Me2Al+ unit had been structurally characterized. 

In this chapter we describe recent developments in the catalytic dehydrogenation of alcohols and related reactions as well as the organometalUc chemistry of rhodium and iridium based on the oxygenation of coordinated alkenes. 

An important recent development in the area of the monodentate amido metal chemistry has come from the group of Cummins who introduced ligands of the type —N(R)Ar (for example, R = Bu , 1-adamantyl (I-Ad), 2-adamantyl (2-Ad), —C(CD3)2(CH3) Ar = Ph, C6H3Me2-3,5, C6H4F-4).These allowed the isolation of an Mo N(R)Ar 3 species having three-coordinate molybdenum as well as three-coordinate derivatives of several other metals. Apart from [M N(SiMe3)2 3] (M = Y," La), the molybdenum compounds are the only examples of structurally characterized open shell, three-coordinate homoleptic amides... 

Since the pioneering work of Gilman and co-workers in the 1960s,1-3 several standard preparative methods have been developed for the synthesis of chain and branched-chain organopolysilanes. More recently, the latter have been used in the design of new dendrimeres4 or cage structures. However, only a few donor-functionalized silanes have found an application in coordination chemistry. 

The great recent development in electrochemical techniques will certainly be helpful for the study of redox processes of a metal which can occur in so many oxidation states. Multinuclear NMR spectrometers will allow increased use of 51V resonance as a routine method for the characterization of complexes in solution. Other recent developments are the study of polynuclear complexes, metal clusters (homo and hetero-nuclear) and mixed valence complexes, and it can be anticipated that these topics will soon become important areas of vanadium coordination chemistry, although the isolation of compounds with such complex... 

This review on the synthesis, properties, and chemistry of coordination complexes will concentrate on the literature since the end of 1985, referring to earlier literature only where relevant. It includes a general survey of recent publications, with more detailed discussions of interesting developments in the latter sections. Analogous Ru chemistry will also be included in particular sections, to show the similarities and differences in the chemistry of these elements. Appropriate literature dealing with organometallic chemistry will be referred to where relevant to the discussion of the coordination chemistry, because Os chemistry often transcends these traditional boundaries. However, no attempt has been made to review recent developments in Os organo-... 

A fairly recent development in zinc and cadmium chemistry has been the use of NMR to study the coordination environment of these metals 1L1Cd, 113Cd and 67Zn nuclei have been A structure-reactivity relationship which predicts formation constants of complexes with organic ligands has been put forward.241 ... 

The early workers in coordination chemistry were more interested in the theory of bonding and structure than in any practical usefulness which the compounds might have. In more recent times, however, applications have developed. Perhaps the most important of these is in catalysis, especially for hydrogenation and the activation of carbon-hydrogen bonds. Metal carbonyls and their derivatives have played a large part in this application, as well as in carbonylation reactions such as the recently developed process for converting methanol to acetic acid 42... 

In view of the widespread use of tertiary phosphines in coordination chemistry, it is somewhat surprising that phosphorus-containing macrocycles have not evoked more interest. In part this is undoubtedly due to experimental difficulties. The synthesis of P macrocycles is doubly difficult, since the usual difficulties and hazards of phosphorus(III) chemistry are compounded by the complexities and low yields of multistage heterocyclic macrocyclic syntheses. Because of these difficulties, the development of synthetic methods has been slow. Mann s survey73 of the heterocyclic derivatives of P, As, Sb and Bi did not mention phosphorus macrocycles and recent textbooks74,75 give them only cursory mention. 

At an early stage in the development of coordination chemistry, tetrahedral and square coplanar geometries were identified. More recently, geometries intermediate between these extremes have been observed. 

---