Synthesis, structure, spectral properties and theoretical studies of two half-sandwich titanium-complexes with adamantoxy ligands

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00474121" target="_blank" >RIV/61388955:_____/17:00474121 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/17:10360424

Výsledek na webu

<a href="http://dx.doi.org/10.1016/j.molstruc.2017.04.072" target="_blank" >http://dx.doi.org/10.1016/j.molstruc.2017.04.072</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molstruc.2017.04.072" target="_blank" >10.1016/j.molstruc.2017.04.072</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis, structure, spectral properties and theoretical studies of two half-sandwich titanium-complexes with adamantoxy ligands

Popis výsledku v původním jazyce

Two novel half-sandwich Ti complexes, both incorporating two adamantoxy (OAd) ligands coordinated to their central atoms were synthesized. The complexes were characterized by H-1, C-13, F-19 NMR, El-MS and IR spectroscopy and by single-crystal X-ray diffraction. In both complexes, the coordination environment is pseudo-tetrahedral and is assembled of two O-coordinated adamantoxy and one eta(5)-coordinated permethylcyclopentadienyl ligand. The fourth ligand in complex 1 is a methyl group coordinated through a regular sigma-bond, whereas in complex 2 the same.coordination site is occupied by the methyl group of the balancing (C6F5)(3)BMe- anion. DFT computations complemented with NBO analyses of 2 have unveiled, that in addition to the electrostatic interactions occurring between the half-sandwich titanocene moiety and the anionic ligand, delocalization of one methyl C-H bond into the available acceptor orbital on the central atom takes place. AIM analyses of 2 have revealed the presence of a Bond Critical Point between the metal atom and the anionic methyl group. These results prove foundation for the description of 2 as a zwitterionic complex coupled with a concurrent Ti...C-H agostic interaction in its molecule. The comparison of 2 with its analogous complex equipped with two Ot-Bu ligands instead of both OAd has suggested only a minor change in the extent of the agostic interaction, despite significant geometric differences between the two complexes.

Název v anglickém jazyce

Synthesis, structure, spectral properties and theoretical studies of two half-sandwich titanium-complexes with adamantoxy ligands

Popis výsledku anglicky

Two novel half-sandwich Ti complexes, both incorporating two adamantoxy (OAd) ligands coordinated to their central atoms were synthesized. The complexes were characterized by H-1, C-13, F-19 NMR, El-MS and IR spectroscopy and by single-crystal X-ray diffraction. In both complexes, the coordination environment is pseudo-tetrahedral and is assembled of two O-coordinated adamantoxy and one eta(5)-coordinated permethylcyclopentadienyl ligand. The fourth ligand in complex 1 is a methyl group coordinated through a regular sigma-bond, whereas in complex 2 the same.coordination site is occupied by the methyl group of the balancing (C6F5)(3)BMe- anion. DFT computations complemented with NBO analyses of 2 have unveiled, that in addition to the electrostatic interactions occurring between the half-sandwich titanocene moiety and the anionic ligand, delocalization of one methyl C-H bond into the available acceptor orbital on the central atom takes place. AIM analyses of 2 have revealed the presence of a Bond Critical Point between the metal atom and the anionic methyl group. These results prove foundation for the description of 2 as a zwitterionic complex coupled with a concurrent Ti...C-H agostic interaction in its molecule. The comparison of 2 with its analogous complex equipped with two Ot-Bu ligands instead of both OAd has suggested only a minor change in the extent of the agostic interaction, despite significant geometric differences between the two complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

Journal of Molecular Structure

ISSN

0022-2860

e-ISSN

—

Svazek periodika

1142

Číslo periodika v rámci svazku

AUG 2017

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

7

Strana od-do

248-254

Kód UT WoS článku

000402357000031

EID výsledku v databázi Scopus

2-s2.0-85018513235