Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to- allene rearrangement, and the electronic transition relevant to the back-bonding interaction

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F15%3A10296267" target="_blank" >RIV/00216208:11310/15:10296267 - isvavai.cz</a>
Alternative codes found
RIV/61388955:_____/15:00443290
Result on the web
<a href="http://dx.doi.org/10.1039/c5dt00351b" target="_blank" >http://dx.doi.org/10.1039/c5dt00351b</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c5dt00351b" target="_blank" >10.1039/c5dt00351b</a>

Result language
angličtina
Original language name
Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to- allene rearrangement, and the electronic transition relevant to the back-bonding interaction
Original language description
The titanocene-ethene complex [Ti((II))(eta(2)-C2H4)(eta(5)-C5Me5)(2)] (1) with simple internal alkynes (RC)-C-1 equivalent to CR2 gives complexes [Ti(II)(eta(2)-(RC)-C-1 equivalent to CR2)(eta(5)-C5Me5)(2)] {R-1, R-2: Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R-1 = Me and R-2 = t-Bu or i-Pr afford allene complexes [Ti(II)(eta(2)-CH2=C=CHR2)(eta(5)-C5Me5)(2)] (11) and (12), whereas for R-2 = Et a mixture of alkyne complex (13A)and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC equivalent to CSiMe3] reversible arrow [8] + [C2H4] approached 1. Compound 9 (R-1, R-2: Me), not obtainable from 1, together with compounds 3-6 and 10 (R1, R2: Et) were also prepared by alkyne
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
<a href="/en/project/GAP207%2F12%2F2368" target="_blank" >GAP207/12/2368: Group 4 metallocenes: activation of ligands for synthetic and catalytic applications</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2015
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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