Chemical bonds, viii

Metals and alloys. The principal industrial metallic catalysts ate found in periodic group VIII which are transition elements with almost completed 3d, 4d, and 5d electron orbits. According to one theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently will depend on the operating conditions. Platinum, palladium, and nickel, for example, form both hydrides and oxides they are effective in hydrogenation (vegetable oils, for instance) and oxidation (ammonia or sulfur dioxide, for instance). Alloys do not always have catalytic properties intermediate between those of the pure metals since the surface condition may be different from the bulk and the activity is a property of the surface. Addition of small amounts of rhenium to Pt/A12Q3 results in a smaller decline of activity with higher temperature and slower deactivation rate. The mechanism of catalysis by alloys is in many instances still controversial. 

Vol. 63 S. Fliszar, Atoms, Chemical Bonds and Bond Dissociation Energies. VIII, 173 pages. 1994. 

Chemical Properties. Organohydrosilanes undergo a wide variety of chemical conversions. The Si—H bond of organohydrosilanes reacts with elements of most groups of the Periodic System, especially Groups 16(VIA) and 17(VIIA). There are no known reactions if the Si—H bond is replaced by stable bonds of sihcon with elements of Groups 2(IIA), 13(IIIA), and 8—10(VIII). 

The rate of reaction of a series of nucleophiles with a single substrate is related to the basicity when the nucleophilic atom is the same and the nucleophiles are closely related in chemical type. Thus, although the rates parallel the basicities of anilines (Tables VII and VIII) as a class and of pyridine bases (Tables VII and VIII) as a class, the less basic anilines are much more reactive. This difference in reactivity is based on a lower energy of activation as is the reactivity sequence piperidine > ammonia > aniline. Further relationships among the nucleophiles found in this work are morpholine vs. piperidine (Table III) methoxide vs. 4-nitrophenoxide (Table II) and alkoxides vs. piperidine (Tables II, III, and VIII). Hydrogen bonding in the transition state and acid catalysis increase the rates of reaction of anilines. Reaction rates of the pyridine bases are decreased by steric hindrance between their alpha hydrogens and the substituents or... 

Group VIII transition metal catalyzed hydrogen exchange reactions are important in providing useful information concerning the fundamental processes of bond rupture and bond formation on catalyst surfaces. The reactions are also a convenient source of deuterated and tritiated compounds for chemical and biological research (i). 

The Zr-H bonds for 7 are clearly hydridic, again in contrast to the group VIII transition metal hydrides that behave chemically more like protonated metal complex anions. Thus 7 readily reduces HCl, CH3I, and CH2O (Reactions 8-10). The Zr+-H- polarization of the zirconium hydride bonds for 7 is not altogether unexpected in light of the position of Zr in the periodic table. 

---