Gas Phase Inorganic Chemistry by Peter B. Armentrout (auth.), David H. Russell (eds.)

By Peter B. Armentrout (auth.), David H. Russell (eds.)

The box of gasoline section inorganic ion chemistry is comparatively new; the early reviews date again nearly two decades, yet there was extreme curiosity and improvement within the box within the final ten years. As with a lot of contemporary chemistry, the expansion in gasoline part inorganic ion chemistry could be traced to the advance of instrumentation and new experimental equipment. experiences during this region require subtle tools and pattern introduc­ tion/ ionization tools, and sometimes those strategies are complex by way of the necessity for state-selecting (or collisionally stabilizing) the reactive species so as to assign the chemistry unequivocally. at present point of experimental improvement, quite a lot of experiments on varied ionic structures are attainable and lots of unique features of the chemistry might be studied. gasoline section Inorganic Chemistry specializes in the reactions of steel ions and steel clusters, and at the research of those species utilizing the on hand glossy spectroscopic equipment. 3 of the twelve chapters hide the chemistry of ionic monometal transition steel ions and the chemistry of those species with small diatomics and version organics. of the chapters concentrate on the reviews of the chemical and actual homes of (primarily) transition steel clusters, and those chapters assessment experimental tools and services. chapters additionally take care of the chemistry of transition steel carbonyl clusters, and those chapters tackle matters vital to cluster development and activation in addition to the characterization of such species.

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Further, the ability to examine the state-specific chemistry of atomic transition metal ions has permitted a reasonably definitive test of the electronic requirements for covalent bond activation. We find that simple molecular orbital ideas can explain this chemistry in a straightforward fashion for H-H, C-H, and C-C bond activation. These ideas are easily related to the electronic requirements outlined in the literature for C-H bond activation. (I) These studies verify that the active metal site must be capable of accepting electron density from the bond to be broken and 40 PETER B.

Cross sections for reaction of Fe+(6D) (open symbols) and Fe+(4F) (closed symbols) with propane to form FeC 2 H; (circles) and FeC 3 Ht (triangles) as a function of relative kinetic energy (lower scale) and laboratory ion energy (upper scale). The dashed line shows uLGs/lO. 35 REACTIONS OF ATOMIC METAL IONS -to products Figure 12. Potential energy surfaces for C-C insertion of Fe+ in propane. Full lines represent adiabatic surfaces and dashed lines represent diabatic surfaces. intermediate H3C-Fe+-C2H5 (IX).

2). Despite the utility of these rules, they clearly can be broken. For instance, the reactivities of the ground states of Sc + and Ti+ do not fall neatly into these categories. This is postulated to be due to mixing of the potential energy surfaces evolving from these states with those from more reactive excited states. Thus, the diabatic rules can fail when adiabatic interactions become important. Note however that the general electronic requirements of donor-acceptor orbitals remain in such cases.

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