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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]

The synthesis of substituted styrenes was achieved by ring-closing enyne metathesis (RCEM)/elimination of enyne substrates 12. The synthetic approach was also effective for a different type of enyne substrate 14, yielding corresponding styrene 15. [ABSTRACT FROM AUTHOR]