Add time:08/09/2019 Source:sciencedirect.com
Bis(propynyl)zirconocene (6a) reacts with tris(pentafluorophenyl)borane to yield the carbon-carbon coupled Cp2M(μ-RC4R)B(C6F5)3 betaine product 4a (M Zr, R CH3). A variety of differently substituted analogs was prepared (M Zr, R = n-butyl, phenyl, cyclohexyl; M Ti, R CH3; M Hf; R CH3, phenyl, SiMe3). These complexes 4 are chiral due to the presence of a rather stable propeller-like RB(aryl)3 conformation. The activation barrier of the intramolecular enantiomerization process of many examples of this series of complexes was determined by dynamic 1H NMR spectroscopy, with †G↕ values ranging from ca. 13 to 16 kcal mol−1, depending on the substitution pattern. Complex 4a reacts with 2,6-dimethylphenylisocyanide to yield the methylenecyclopropene derivative 1 that was characterized by X-ray diffraction.
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