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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(eta(5)-C5HMe4)(mu-eta(1) : eta(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 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.

Název v anglickém jazyce

Sunlight-induced dehydrogenation rearrangement of the dititanium complex [Ti(eta(5)-C5HMe4)(mu-eta(1) : eta(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 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical 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

1872-8561

Svazek periodika

934

Číslo periodika v rámci svazku

FEB 2021

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