Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(eta(5)-C5HMe4)(mu-eta(1) : eta(5)-C5Me4)](2)
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00538224" target="_blank" >RIV/61388955:_____/21:00538224 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0316048" target="_blank" >http://hdl.handle.net/11104/0316048</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1016/j.jorganchem.2020.121663" target="_blank" >10.1016/j.jorganchem.2020.121663</a>
Alternative languages
Result language
angličtina
Original language name
Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(eta(5)-C5HMe4)(mu-eta(1) : eta(5)-C5Me4)](2)
Original language description
Sunlight photolysis of the triplet state (S = 1) dititanium compound 1 induced its rearrangement to diamagnetic 2, which was a molecule containing two hydrogens less. The cage structure of 2 was determined by single crystal X-ray diffraction and was corroborated fully by 1H and 13C NMR spectra that identified three simple bridging moieties — a hydrogen atom, a methine carbon and a methylene carbon. Its extremely short Ti−Ti distance 2.7537(7) Å causes a strong distortion of the bridging fulvalene ligand, which becomes η5- bonded to one Ti(IV) and connected by two σ-bonds from nearest carbon atoms of its other ring to the other Ti(IV) of 2. Other photolytical byproducts in very minor amounts were also isolated, which differed from 2 by the absence of one bridging moiety: compound 4 lacked the methine group and compound 5 had no bridging hydrogen. In the latter cases, the Ti−Ti distance fell in the range 3.2077(8) – 3.5543(12) Å and the fulvalene ligand was coordinated in the common µ-η5: η5-mode to both titanium atoms. The octamethylfulvalene ligands in 4 and 5 had their ring planes rotated mutually by about 40° in order to relieve the steric hindrance between their methyl groups. The thermally robust µ-oxo complex 3 obtained from reacting 2 with water showed a very similar structure.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2021
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Organometallic Chemistry
ISSN
0022-328X
e-ISSN
1872-8561
Volume of the periodical
934
Issue of the periodical within the volume
FEB 2021
Country of publishing house
CH - SWITZERLAND
Number of pages
10
Pages from-to
121663
UT code for WoS article
000612238600001
EID of the result in the Scopus database
2-s2.0-85098589151