Transition metals chemical reactivity

With the advent of appropriate DFT-based methods, NMR properties of transition-metal compounds have now become amenable to theoretical computations (8). Suitable density functionals have been identified (9) which permit calculations of transition-metal chemical shifts with reasonable accuracy, typically within a few percent of the respective shift ranges. Thus, it is now possible to investigate possible NMR/reactivity correlations for transition-metal complexes from first principles several such studies have already been undertaken (10,11,12). 

The microscopic understanding of tire chemical reactivity of surfaces is of fundamental interest in chemical physics and important for heterogeneous catalysis. Cluster science provides a new approach for tire study of tire microscopic mechanisms of surface chemical reactivity [48]. Surfaces of small clusters possess a very rich variation of chemisoriDtion sites and are ideal models for bulk surfaces. Chemical reactivity of many transition-metal clusters has been investigated [49]. Transition-metal clusters are produced using laser vaporization, and tire chemical reactivity studies are carried out typically in a flow tube reactor in which tire clusters interact witli a reactant gas at a given temperature and pressure for a fixed period of time. Reaction products are measured at various pressures or temperatures and reaction rates are derived. It has been found tliat tire reactivity of small transition-metal clusters witli simple molecules such as H2 and NH can vary dramatically witli cluster size and stmcture [48, 49, M and 52]. 

The reactivity of size-selected transition-metal cluster ions has been studied witli various types of mass spectrometric teclmiques [1 ]. Fourier-transfonn ion cyclotron resonance (FT-ICR) is a particularly powerful teclmique in which a cluster ion can be stored and cooled before experimentation. Thus, multiple reaction steps can be followed in FT-ICR, in addition to its high sensitivity and mass resolution. Many chemical reaction studies of transition-metal clusters witli simple reactants and hydrocarbons have been carried out using FT-ICR [49, 58]. 

Chemical Properties. Higher a-olefins are exceedingly reactive because their double bond provides the reactive site for catalytic activation as well as numerous radical and ionic reactions. These olefins also participate in additional reactions, such as oxidations, hydrogenation, double-bond isomerization, complex formation with transition-metal derivatives, polymerization, and copolymerization with other olefins in the presence of Ziegler-Natta, metallocene, and cationic catalysts. All olefins readily form peroxides by exposure to air. 

Chemical reactivity of higher fluorides of the transition metals. T. A. O Donnell, Rev. Pure Appl. Chem., 1970, 20,159-174(56). 

Because of the unambiguous reactive sites of monomers and the high chemo-and stereoselectivity of transition-metal-catalyzed coupling reactions, polymers prepared by transition metal coupling have predictable chemical structures. Functional groups can be easily and selectively introduced at the desired position within die polymer chains. Therefore, polymers widi specific properties can be rationally designed and synthesized. 

For the mechanism of azolide hydrolysis under specific conditions like, for example, in micelles,[24] in the presence of cycloamyloses,[25] or transition metals,[26] see the references noted and the literature cited therein. Thorough investigation of the hydrolysis of azolides is certainly important for studying the reactivity of those compounds in chemical and biochemical systems.[27] On the other hand, from the point of view of synthetic chemistry, interest is centred instead on die potential for chemical transformations e.g., alcoholysis to esters, aminolysis to amides or peptides, acylation of carboxylic acids to anhydrides and of peroxides to peroxycarboxylic acids, as well as certain C-acylations and a variety of other preparative applications. 

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