Vibrational Spectra and Electronic Structure of Germatranols (HO)(4-n) Ge(OCH2CH2)(n)NR3 (-) (n) (R = H; n = 1-3) with Transannular Ge⋯N Bonding | Sciact - CRIS-система Института катализа

Vibrational Spectra and Electronic Structure of Germatranols (HO)(4-n) Ge(OCH2CH2)(n)NR3 (-) (n) (R = H; n = 1-3) with Transannular Ge⋯N Bonding Научная публикация

Журнал

Journal of Organometallic Chemistry
ISSN: 0022-328X

Вых. Данные

Год: 2013, Том: 747, Страницы: 62-68 Страниц : 7 DOI: 10.1016/j.jorganchem.2012.12.036

Ключевые слова

DFT, Electronic structure, Germatranols, Molecular structure, Vibrational spectrum

Авторы

Ignatyev I.S. ¹ , Samokhin G.S. ² , Kochina T.A. ² , Belyaeva V.V. ³ , Khaikin S.Ya. ⁴ , Montejo M. ⁵ , González J.J.López ⁵ , Voronkov M.G. ²

Организации

1	Department of Chemistry, Radiochemistry Laboratory, St. Petersburg State University, 199034 St. Petersburg, Russia
2	Grebenshchikov Institute of Silicate Chemistry RAS, 199034 St. Petersburg, Russia
3	Favorsky Institute of Chemistry SB RAS, Irkutsk, Russia
4	Boreskov Institute of Catalysis (St. Petersburg Branch), SB RAS, 199034 St. Petersburg, Russia
5	Department of Physical and Analytical Chemistry, University of Jaén, Campus “Las Lagunillas”, E-23071 Jaén, Spain

Series of germatrane compounds with OH functionality and Ge⋯N transannular bonding, i.e. 1-germatranol (I), 1,1-quasigermatranol (II) and 1,1,1-hypogermatranol (III) with general formula (HO)4 − nGe(OCH2CH2)nNR3 − n (R = H, Me; n = 1–3) are synthetized and their solid state IR spectra are recorded. Equilibrium structures and vibrational spectra of monomeric and centrosymmetric dimeric species of these compounds are predicted by the DFT B3LYP/aug-cc-pVDZ method. The assignment of the vibrational spectra of I–III was carried out based on theoretical IR spectra scaled with factors obtained earlier for halogermatranes to take account of the substantial and systematic discrepancy between Ge⋯N interatomic distance of the gas phase and theoretical predictions on the one hand and X-ray solid state data on the other. Dimeric models provide a good agreement between experimental and predicted frequencies, including GeOH bending modes, of I, crystalline state of which is formed by dimers, and slightly worse for II, in which some weaker O–H⋯O and N–H⋯O hydrogen bonds are not considered in the dimeric model. However, this model for III is poor since it does not take into account hydrogen bonding of “free” OH and NH2 groups. Despite the steady decrease of the Ge⋯N interatomic distance, corresponding frequencies demonstrate the substantial increase on going from I to II and practically no increase from II to III.

Ignatyev I.S. , Samokhin G.S. , Kochina T.A. , Belyaeva V.V. , Khaikin S.Y. , Montejo M. , González J.J.L. , Voronkov M.G.
Vibrational Spectra and Electronic Structure of Germatranols (HO)(4-n) Ge(OCH2CH2)(n)NR3 (-) (n) (R = H; n = 1-3) with Transannular Ge⋯N Bonding
Journal of Organometallic Chemistry. 2013. V.747. P.62-68. DOI: 10.1016/j.jorganchem.2012.12.036 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	20 нояб. 2012 г.
Принята к публикации:	19 дек. 2012 г.
Опубликована online:	3 янв. 2013 г.
Опубликована в печати:	1 дек. 2013 г.

Web of science:	WOS:000326116500009
Scopus:	2-s2.0-84887119764
РИНЦ:	21887515
Chemical Abstracts:	2013:147606
Chemical Abstracts (print):	159:726956
OpenAlex:	W1965253513

БД	Цитирований
Web of science	7
Scopus	8
OpenAlex	8