Search

Hyperthermal collisions of ground-state atomic oxygen with H2O have been investigated, with special attention paid to the H-atom elimination reaction, O(3P) H2O(X 1A1) → HO2(2A‘) H(2S). This reaction was observed in a crossed-beams experiment, and the relative excitation function in the region around its energy threshold (50−80 kcal mol-1) was measured. Direct dynamics calculations were also performed at two levels of theory, B3LYP/6-31G(d,p) and MP2/6-31G(d,p). The shape of the B3LYP excitation function closely matches that of the experiment. The calculations provided a detailed description of the dynamics and revealed a striking dependence of the reaction mechanism on collision energy, where the cross section rises from a threshold near 60 kcal mol-1to a peak at ∼115 kcal mol-1and then decreases at higher energies as secondary dissociation of the internally excited HO2product becomes dominant. The calculations show that the cross section for H-atom elimination (O H2O → HO2H) is about 10−25% that of the H-atom abstraction (O H2O → OH OH) cross section for collision energies in the 70−160 kcal mol-1range. [ABSTRACT FROM AUTHOR]

Heck-type 4-exo-trigcyclization of linear 2-enol triflate-1,5-hexadienes provides functionalized methylene cyclobutanes. Intramolecular palladium coordination can initiate -hydride elimination leading to 1,2-dimethylene cyclobutane derivatives, which are obtained with high selectivity if substrates having a geminal diphenyl group at Care used. In parallel, formal 5-endo-trigcyclization and -hydride elimination form 1-methylene cyclopent-2-en derivatives. [ABSTRACT FROM AUTHOR]

A five-step preparation of carbohydrate-based oxepines from hept-l-enitols is presented. The hept-l-enitols were subjected to silyl protection and hydroboration/oxidation to give the protected heptan-1-itols. Swern oxidation of the homologated alcohols followed by sequential acetal formation/ cyclization provided methyl 2-deoxyseptanosides that underwent elimination reactions to give the carbohydratebased oxepines. The new sequence is an alternative to the ring-closing metathesis for the synthesis of carbohydratebased oxepines from protected pyranose sugars. The product oxepines can serve as glycosyl donors in the synthesis of novel septanose carbohydrates. In addition, C-methylenealdehydo arabinofuranoside 16 was formed from 2-deoxyseptanoside 10 as the only product during protic acid mediated elimination reactions. This novel ring contraction complements other reported preparations of C-methylenaldehydo furanosides and underscores the acid-mediated reactivity introduced by competing eliminations between the C-1/C-2 and C-2/C-3 bonds. [ABSTRACT FROM AUTHOR]

Exposure of a series of zirconocene amido and hydrazido hydride complexes, (η 5-C 5Me 4H) 2Zr(NHR)H (R = tBu, NMe 2, Me, H), to 4 atm of D 2gas at 56 °C produced isotopic exchange in both the N−H and Zr−H positions. In general, the relative rates of 1,2-elimination can be rationalized on the basis of ground-state effects, whereby amido compounds with the strongest N−H bonds, as judged by the corresponding free amine, undergo the slowest isotopic exchange. For the compound with the strongest N−H bond in the series, (η 5-C 5Me 4H) 2Zr(NH 2)H, the barrier for 1,2-elimination is sufficiently high such that σ-bond metathesis becomes the dominant intermolecular exchange pathway. For the other amido zirconocene hydrides, the rate constants for deuterium exchange into the N−H position are faster than for the Zr−H position. This behavior is a result of a faster intramolecular isomerization process driven by an equilibrium isotope effect favoring N−D over Zr−D bond formation. Computational studies on a related model compound, (η 5-C 5H 5) 2Zr(NH tBu)H, successfully reproduce these observations and support a pathway involving the formation of rare d 0dihydrogen complexes. [ABSTRACT FROM AUTHOR]