Coordination chemistry reactivity

The synthesis and characterization of phosphorus-based ligands continues to receive considerable attention on account of their diverse coordination chemistry, reactivities, and applications, principally in the field of homogeneous catalysis. Such spectacular interest in this fascinating class of ligand stems from the ease with which important properties of the ligand can be finely manipulated, as reflected by many of the examples cited here. Without doubt, phosphorus chemistry will continue to develop in the foreseeable future, with many diverse and interesting compounds yet to be discovered. 

Coordination Chemistry, Reactivity, and Applications of Early Transition Metal Complexes Bearing A/-Heterocyclic Carbene Ligands... 

Butler A, Theisen RM (2010) Siderophore coordination chemistry reactivity of marine siderophores. Chem Rev 254 288—296... 

Very recently, the coordination chemistry of low valent silicon ligands has been established as an independent, rapidly expanding research area. With the discovery of stable coordination compounds of silylenes [35-38], a major breakthrough was achieved. Within a short time a variety of stable complexes with a surprising diversity of structural elements was realized. Besides neutral coordination compounds (A, B) [35, 36, 38], and cationic compounds (C) [37], also cyclic bissilylene complexes (D) [39,40] exist. A common feature of the above-mentioned compounds is the coordination of an additional stabilizing base (solvent) to the silicon. However, base-free silylene complexes (A) are also accessible as reactive intermediates at low temperatures. 

The trivalent Co coordination chemistry of amines is simply immense. Amines, both mono- and multidentate, are typically thermally and air stable, often commercially available, easily deriva-tized, and are well matched to the electronic needs of trivalent Co. Space does not permit a discussion of all categories of amines that have been investigated since CCC(1987) nor their limitless permutations when bound to mostly six-coordinate Co. Much of the synthetic and mechanistic work that underpins Co amine chemistry has long been known and will not be restated here. The emphasis here will be on novelty rather than breadth. That is, recent innovative aspects of the structure, reactivity, and applications of selected, but representative, collections of these simple but ever-present compounds will be our focus. 

Metalloporphyrin reactivity and catalytic properties can also be controlled by modifications of the porphyrin core. Ni coordination chemistry of core-modified porphyrins has been reviewed.1791,1792 Several X-ray structures of four-, five-, and six-coordinate Ni11 complexes with oxa-, thia-, and dioxatetraarylporphyrins are known. 

Acknowledging the important part that 99mTc(V) radiopharmaceuticals are playing in nuclear medicine, advances in their coordination chemistry, as attained by new syntheses and better structural characterization, are discussed with respect to the design of Tc(V) radiotracers. In the light of current interest in making technetium complexes active in vivo, a chapter considering several aspects of reactivity is included. 

Metal sulfides and polysulfides have been extensively studied because of their key role in important catalytic processes such as the hydrodesulfurization of crude oil or the biosynthesis of metalloproteins. The coordination chemistry of polysulfides85 86 has been comprehensively reviewed similar to that of the heavier polychalcogenides.10,12 15 Polysullido complexes are themselves reactive and their exothermic desulfurization can be exploited as a means of... 

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