Transition metal reactivity

Keywords. Phosphinidene, P chemistry. Transition metal. Reactive intermediate, Fischer,... 

In particular, reactions involving transition-metals have attracted a lot of interest recently because of the connection to catalytic and enzymatic processes. Unfortunately, the proper computational description of such reactions is one of the great challenges of today s theoretical chemistry and the question for the general applicability of density functional methods in the field is an area of active research. We chose to provide a single but - as we think - representative example to illustrate the difficulties one has to face in theoretical studies of transition-metal reactivity. 

The Role of Vibrational Excitation in Transition Metal Reactivity 268... 

One of the surprising aspects of this and other studies using naked metal ions as models for electron-transfer catalysis are the many analogies found to known transition metal chemistry, either in the gas phase with naked ions or for complexes under more normal conditions. Clearly, such simple models as the beryllium cation cannot account for transition metal reactivity, but they do have the advantage that, because of their very simplicity, the reasons for their effects are relatively clear. The fact that Be can catalyze a given reaction does not necessarily mean that, for instance, a transition metal does not use d-orbitals to catalyze the same reaction but it does mean that d-orbitals are not a prerequi-... 

TAMREAC (TrAnsition Metal REACtivity) is written in FORTRAN and runs on a PDP 11/44 computer. The program is interactive and allows facile graphical communication of both input and output in a form most convenient... 

Beyond the Harpoon Model the HOMO/LUMO Matching to Describe Transition Metal Reactivity... 

Poll R. Relationship between one-electron transition-metal reactivity and radical polymerization processes. Angew Chem Int Ed 2006 45 5058-5070. 

Contents Comparison of synthetic reactions by transition metal complexes with those by Grignard reagents. -Formation of a-bond involving transition metals. -Reactivities of a-bonds involving transition metals. -Insertion reactions. - Liberation of organic compounds from the a-bonded complexes. - Cyclization reactions, and related reactions. - Concluding remarks. 

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