Synthesis, structure, and reactivity of mixed-sandwich zirconacarborane methyl complex (eta(5)-C5Me5)[eta(1):eta(5)-(Me2NCH2CH2)C2B9H10]ZrMe
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AbstractA neutral mixed-sandwich zirconacarborane methyl complex (eta(5)-Cp*)[eta(1): eta(5)-(Me2NCH2CH2)C2B9H10]Zr(Me) (1) (Cp* = C5Me5) was prepared via methane elimination reaction of 7-Me2N(H)CH2CH2-7,8-C2B9H11 with (eta(5)-Cp*)ZrMe3. It underwent intramolecular CeH activation at 70 degrees C to afford [eta(1): sigma: eta(5-){MeN(CH2)CH2CH2}C2B9H10]Zr(eta(5)-Cp*) (2) and eliminate CH4. This complex reacted with internal alkynes to give the Zr-C sigma bond mono-insertion products, in which both electronic and steric factors played a role in controlling the regioselectivity of the insertion process. In the case of terminal alkynes, both insertion and acid-base reaction products were obtained, dependent upon the substituents. On the other hand, complex 1 reacted with alkyl nitriles at room temperature to give the mono-insertion zirconacarborane imide complexes, whereas high temperature was required to promote the insertion reaction with aryl nitrile, generating a different type of insertion product, zirconacarborane amide. All new complexes were characterized by NMR spectroscopy and elemental analyses. Most of them were further confirmed by single-crystal X-ray analyses.
Acceptance Date23/08/2016
All Author(s) ListDongmei Liu, Zaozao Qiu, Zuowei Xie
Journal nameJournal of Organometallic Chemistry
Volume Number822
Pages144 - 153
LanguagesEnglish-United Kingdom
KeywordsAlkyne, Carborane, Insertion, Nitrile, Zirconacarborane
Web of Science Subject CategoriesChemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic

Last updated on 2021-08-06 at 01:18