Structural Diversity of New Polynuclear Self-Assembled Organometallogermoxanes
Доклады на конференциях
27th International Chugaev Conference on Coordination Chemistry and 4th Young Conference School “Physicochemical Methods in the Chemistry of Coordination Compounds”
02-06 окт. 2017
Международная конференция, Нижний Новоород
|| Корлюков Александр А.
, Вологжанина Анна Владимировна
, Хрусталев Виктор Н.
, Воронова Евгения Дмитриевнa
, Белякова Ольга Алексеевна
, Головешкин А. С.
, Кулакова Алена Н.
, Биляченко Алексей Николаевич
Институт элементоорганических соединений им. А.Н.Несмеянова РАН
Российский университет дружбы народов
Organometallogermoxanes is the new class of polynuclear clusters with atoms of transition and rare-earth metals. From structural point of view compound of this family can be described as closest analogues of organometallosiloxanes . Indeed, silicon and germanium atoms have very close covalent radii, so it is reasonable to expect similar cluster frameworks formed by RSi(Ge)O3 moieties. To prepare the compounds under consideration we used the synthetic route similar to that for organometallosiloxanes. The hydrolysis of RGe(OR’) 3 (R = Ph, R’ = Me) with subsequent addition of transition or rare-earth metal chlorides in polar solvents afforded the number of polynuclear complexes containing several metal atoms and macrocyclic organogermanium ligands . Our X-ray diffraction studies have shown that the nature of transition (or rare-earth) metal atoms is the principle factor responsible for the shape of polynuclear cage and the amount of macrocyclic organogermanium ligands. Thus, herein we report crystal structures of title compounds and discuss their structural diversity in comparison with organometallosiloxanes. In addition, especial attention will be paid to the size of organogermanium ligands. As a rule, the majority of studied organometallogermoxanes contains the decamembered [RGeO1.5]5 ligand while in the case of its silicon analogues the twelvemembered ligand [RSiO1.5]6 is the most abundant. To give insight on the problem of stability of macrocyclic anionic organosilicon and organogermanium ligands and some aspect of their self-assembling theoretical DFT calculations were carried out. The final point of our presentation is the design of coordination polymers and other types of supramolecular architectures constructed via weak interactions (H-bonds or stacking interactions).
 M. M. Levitsky, A. N. Bilyachenko, Coord. Chem. Rev. 2016, 306, 235-269  A. N. Bilyachenko et al., Angew Chem. Int. Ed. 2016, 55 (49), 15360–15363.
Acknowledgements - RFBR for financial support (project nos 16-29-05180, 16-03-00609 и 16-03-00206) and the Ministry of Education and Science of the Russian Federation (Agreement No. 02.a03.21.0008), Dr. Y. V. Zubavichus (Kurchatov center for synchrotron radiation and nanotechnology) for the help in single-crystal synchrothron X-ray studies.