Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(η(5)-C5HMe4)(μ-η(1) : η(5)-C5Me4)](2)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F21%3A10427959" target="_blank" >RIV/00216208:11310/21:10427959 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=MoeAP-SsJ1" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=MoeAP-SsJ1</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>

Jazyk výsledku

angličtina

Název v původním jazyce

Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(η(5)-C5HMe4)(μ-η(1) : η(5)-C5Me4)](2)

Popis výsledku v původním jazyce

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 (1)H and (13)C 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 η(5)- bonded to one Ti(IV) and connected by two sigma-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-η(5) : η(5)-mode to both titanium atoms. The octamethylfulvalene ligands in 4 and 5 had their ring planes rotated mutually by about 40 degrees 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.

Název v anglickém jazyce

Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(η(5)-C5HMe4)(μ-η(1) : η(5)-C5Me4)](2)

Popis výsledku anglicky

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 (1)H and (13)C 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 η(5)- bonded to one Ti(IV) and connected by two sigma-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-η(5) : η(5)-mode to both titanium atoms. The octamethylfulvalene ligands in 4 and 5 had their ring planes rotated mutually by about 40 degrees 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

—

Svazek periodika

934

Číslo periodika v rámci svazku

February

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

10

Strana od-do

121663

Kód UT WoS článku

000612238600001

EID výsledku v databázi Scopus

2-s2.0-85098589151