By Ryschkewitsch G.E.

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PETER B. ARMENTROUT 30 ENERGY ( .. V, Lab) 0. O • 2. 0 ENERGY ( .. V, .. 0 eM) Figure 8 Cross sections for reaction of Sc+ (produced by surface ionization) with ethane as a function of relative kinetic energy (lower scale) and laboratory ion energy (upper scale). The dashed line shows a L Gs/50. 1) does not. This type of barrier has also been noted by ab initio calculations for reductive elimination from HPdCH 3 (barrier height = 10 kcaljmol) and HPdH (2 kcaljmol) . (5 6) The reason for the increased barrier in the former case is that the Sp3 orbital on the methyl radical is directional.

10) The application of these techniques to other types of metal-ligand systems is also a limitless area of expansion in which work is already under way. 2. Reactions with Dihydrogen The experimental results and theoretical considerations discussed in Section 4 lead to a reasonably comprehensive view of the reactions of atomic REACTIONS OF A TOMIC METAL IONS 37 transition metal ions with molecular hydrogen. Three categories of reactivity appear to exist based on the electron configuration and spin state of the metal: 1.

This changes the population of the S D and sF states very little (Table 0, but the 3 F population varies by over a factor of 2. The magnitude of the exothermic part of the process in Equation 20 tracks with this variation. 4 eY, the quintet states also begin to form YC 2H;. In retrospect, this result may not be so surprising. Based on the mechanisms discussed above, dehydrogenation should occur via insertion into a C-H bond of ethane to form H-Y+-C 2Hs (YI). Since two of the four electrons on the metal are involved in binding the H and ethyl radical ligands, only two unpaired electrons remain on the metal ion.

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