trans-W(Cmesityl)(dmpe)2H: revealing a highly polar W-H bond and H-mobility in liquid and solid state.

The isotopomeric complexes trans-W(Cmesityl)[(C(H,D)3)2PCH2CH2P(C(H,D)3)2]2(H,D) 1-4 were prepared. 2 (W(Cmesityl)(dmpe)2D) was used to study the Deuterium Quadrupole Coupling Constant (DQCC) and the ionicity of the W-D bond (DQCC=34.1 kHz; ionicity 85%). 1 (W(Cmesityl)(dmpe)2H) shows several dynamic exchange processes in solution, such as HW/HW, HW/ortho-Memesityl, and HW/H2 exchanges observed by NMR in combination with deuterium labeling studies and double label crossover experiments. Except for the HW/H2, these reactions comprise elementary steps, which also appear along the isomerization pathway of 1 into (2,3,5-trimethylphenylcarbyne)(dmpe)2WH (5) at 60 degrees C. 5 was characterized by an X-ray diffraction study. In the solid state only an HW/Mep exchange process prevails appearing at higher temperatures, which was identified by NMR and by Quasielastic Neutron Scattering. The latter also provided an activation barrier of 5 kcal/mol and a "jump width" for the moving H nucleus in agreement with the HW...Mep distance of the X-ray diffraction study of 1.

Synthesis and structures of cycloalkylidene-bridged cyclopentadienyl metallocene catalysts: effects of the bridges of ansa-metallocene complexes on the catalytic activity for ethylene polymerization.

A series of cycloalkylidene-bridged cyclopentadienyl metallocene complexes, [(CH(2))(n)C(C(5)H(4))(2)MCl(2)] (M = Ti, n = 4 (4), 5 (5), 6 (6); M = Zr, n = 4 (7), 5 (8), 6 (9); M = Hf, n = 4 (10), 5 (11), 6 (12)), have been synthesized and applied to ethylene polymerization after activation with methyl aluminoxane (MAO). The cycloalkylidene-bridged titanocene catalysts exhibit much higher activities than the corresponding zirconocene and hafnocene analogues, and have the highest activities at higher temperatures. In comparison, the silacyclopentylidene-bridged metallocene complexes [(CH(2))(4)Si(C(5)H(4))(2)MCl(2)] (M = Ti (13), Zr (14)) and isopropylene-bridged metallocene complexes [Me(2)C(C(5)H(4))(2)MCl(2)] (M = Ti (15), Zr (16)) have also been synthesized and applied to ethylene polymerization. In both cases, the titanocene complexes show much higher activities than the corresponding zirconocene analogues, especially at a lower temperature. The molecular structures of complexes 4-9 have been determined by X-ray diffraction. The structure-activity relationships, especially the effects of the bridges of ansa-metallocene complexes, are discussed.