Photochemistry of Dithiocarbamate Cu(S2CNEt2)2 Complex in CHCl3. Transient Species and TD-DFT Calculations | Sciact - CRIS-система Института катализа

Photochemistry of Dithiocarbamate Cu(S2CNEt2)2 Complex in CHCl3. Transient Species and TD-DFT Calculations Научная публикация

Журнал

The Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215

Вых. Данные

Год: 2016, Том: 120, Номер: 40, Страницы: 7873-7880 Страниц : 8 DOI: 10.1021/acs.jpca.6b08738

Ключевые слова

Continuum mechanics; Coordination reactions; Dimers; Metal ions; Molecules; Photolysis; Quantum chemistry

Авторы

Solovyev Aleksey I. ^1,2 , Plyusnin Victor F. ^1,2 , Shubin Aleksandr A. ^2,3 , Grivin Vjacheslav P. ¹ , Larionov Stanislav V. ^2,4

Организации

1	Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia
2	Novosibirsk State University, 630090 Novosibirsk, Russia
3	Boreskov Institute of Catalysis SB RAS, 630090 Novosibirsk, Russia
4	Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia

Информация о финансировании (2)

1	Российский фонд фундаментальных исследований	14-03-00692
2	Российский фонд фундаментальных исследований	14-03-00212

Nanosecond laser flash photolysis was used to study the mechanism of photochemical transformations of the diethyldithiocarbamate Cu(II) complex (Cu(dtc)2, where dtc− ≡ −S2CNEt2 anion) in chloroform solutions. The electron transfer from the excited Cu(dtc)2 complex to a solvent molecule leads to the appearance of the primary intermediate, the [ClCu(dtc)(dtcCHCl2)] complex, where a dtcCHCl2 molecule is coordinated with a copper ion via one sulfur atom. In the fast reaction (k= 2.1 × 109 M−1 s−1) with Cu(dtc)2, this complex forms a long-lived dimer [ClCu(dtc)(dtcCHCl2)Cu(dtc)2]. This intermediate decays during several seconds (k = 5.6 × 10−2 s−1) into the final product, i.e., a diamagnetic dimer [ClCu(dtc)Cu(dtc)2]. To determine the structure of intermediate complexes the quantum chemical calculations were carried out using DFT, TD-DFT, and PCM (Polarizable Continuum Model) methods.

Solovyev A.I. , Plyusnin V.F. , Shubin A.A. , Grivin V.P. , Larionov S.V.
Photochemistry of Dithiocarbamate Cu(S2CNEt2)2 Complex in CHCl3. Transient Species and TD-DFT Calculations
The Journal of Physical Chemistry A. 2016. V.120. N40. P.7873-7880. DOI: 10.1021/acs.jpca.6b08738 WOS Scopus РИНЦ CAPlusCA PMID OpenAlex

Поступила в редакцию:	30 авг. 2016 г.
Опубликована online:	30 сент. 2016 г.
Опубликована в печати:	13 окт. 2016 г.

Web of science:	WOS:000385606800010
Scopus:	2-s2.0-84991640194
РИНЦ:	27583398
Chemical Abstracts:	2016:1519301
Chemical Abstracts (print):	165:470302
PMID (PubMed):	27632377
OpenAlex:	W2519820504

БД	Цитирований
Web of science	11
Scopus	12
РИНЦ	11
OpenAlex	10