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- W1963533883 abstract "(η4-Isoprene)zirconocene reacts with hexacarbonyltungsten to give the metallacyclic (π-allyl)zirconoxycarbene complex Cp2ZrOC[W(CO)5]CH2CHC(CH3)CH2 (14a), the structure of which has been determined by an X-ray diffraction study. Only one regioisomer is formed, that with the methyl substituent at the meso-position (C2) of the π-allyl-carbene ligand chain. Complex 14a undergoes insertion of one equivalent of acetone to give the nine-membered metallacyclic zirconoxycarbene complex Cp2ZrOC[W(CO)5]CH2CHC(CH3)CH2CR1R2O (18, R1 = R2 = CH3), which has an E-configurated endocyclic CC double bond. The chiral metallacycle 18 undergoes a thermally induced intramolecular enantiomerization, the activation barrier for which has been determined by dynamic 1H NMR spectroscopy to be ΔGent≠ (280 K) = 14.3 ± 0.3 kcal/mol. With pinacolone, 14a forms an analogous nine-membered metallacyclic zirconoxycarbene complex (only one diastereoisomer observed under thermodynamic control), which undergoes a stereo-unselective base-induced α-alkylation reaction to yield a 55/45 mixture of diastereomeric C6-monomethylated carbene complexes." @default.
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- W1963533883 date "1990-08-01" @default.
- W1963533883 modified "2023-10-01" @default.
- W1963533883 title "Zirconoxycarbene complexes obtained by regioselective coupling of (isoprene)zirconocene with hexacarbonyltungsten and a ketone. Crystal structure of Cp2H2" @default.
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- W1963533883 doi "https://doi.org/10.1016/0022-328x(90)87227-5" @default.
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