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Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene

Maxim Vladimirovich Andreev 1
Maxim Vladimirovich Andreev
, 
Vyacheslav Sergeevich Bogdanov 1
Vyacheslav Sergeevich Bogdanov
, 
Mikhail Alekseevich Frolov 1
Mikhail Alekseevich Frolov
, 
Elizaveta Ruslanovna Nurzhanova 1
Elizaveta Ruslanovna Nurzhanova
, 
Alexander Fedorovich Smol'yakov 1, 2
Alexander Fedorovich Smol'yakov
, 
Vladimir Vasil'evich Burlakov 1
Vladimir Vasil'evich Burlakov
1 A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Moscow, Russian Federation
2 Peoples Friendship University of Russia (RUDN University), Moscow, Russian Federation
10.1016/j.mencom.2023.10.003
Published 2023-10-18
Communication , Volume 33, Issue 6, 750-752
2
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Andreev M. V. et al. Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene // Mendeleev Communications. 2023. Vol. 33. No. 6. pp. 750-752.
GOST all authors (up to 50) Copy
Andreev M. V., Bogdanov V. S., Frolov M. A., Nurzhanova E. R., Smol'yakov A. F., Burlakov V. V. Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene // Mendeleev Communications. 2023. Vol. 33. No. 6. pp. 750-752.
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TY - JOUR
DO - 10.1016/j.mencom.2023.10.003
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.10.003
TI - Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene
T2 - Mendeleev Communications
AU - Andreev, Maxim Vladimirovich
AU - Bogdanov, Vyacheslav Sergeevich
AU - Frolov, Mikhail Alekseevich
AU - Nurzhanova, Elizaveta Ruslanovna
AU - Smol'yakov, Alexander Fedorovich
AU - Burlakov, Vladimir Vasil'evich
PY - 2023
DA - 2023/10/18
PB - Mendeleev Communications
SP - 750-752
IS - 6
VL - 33
ER -
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@article{2023_Andreev,
author = {Maxim Vladimirovich Andreev and Vyacheslav Sergeevich Bogdanov and Mikhail Alekseevich Frolov and Elizaveta Ruslanovna Nurzhanova and Alexander Fedorovich Smol'yakov and Vladimir Vasil'evich Burlakov},
title = {Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene},
journal = {Mendeleev Communications},
year = {2023},
volume = {33},
publisher = {Mendeleev Communications},
month = {Oct},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.10.003},
number = {6},
pages = {750--752},
doi = {10.1016/j.mencom.2023.10.003}
}
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Andreev, Maxim Vladimirovich, et al. “Protolysis of five-membered metallacyclocumulene complexes of zirconocene and hafnocene.” Mendeleev Communications, vol. 33, no. 6, Oct. 2023, pp. 750-752. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.10.003.
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Keywords

enyne.
hafnium
metallacycloallene
metallacyclocumulene
zirconium

Abstract

The reactions of the five-membered metallacyclocumulene complexes Cp2M[η4ButC4But] (M = Zr, Hf) with an equimolar amount of HCl in dioxane at 20 °C result in linear complexes Cp2M(Cl)-C(But)=CH-C≡CBut, whereas the reaction with an excess of HCl affords Cp2MCl2 and trans-ButCH=CH-C≡CBut. The reaction of the latter hydrocarbon with an equivalent amount of the bis(trimethylsilyl)acetylene complex of zirconocene Cp2Zr(Me3SiC2SiMe3)(Py) leads to bis(trimethylsilyl)acetylene and a five-membered zircona-cycloallene complex. This complex can also be obtained in ‘one-pot’ via the reactions of five-membered zircona-cyclocumulene with two equivalents of HCl and subsequent treatment with magnesium in THF.

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