Photochemistry of Dithiophosphinate Ni(S2P(i-Bu)2)2 Complex in CCl4. Transient Species and TD-DFT Calculations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Photochemistry of Dithiophosphinate Ni(S2P(i-Bu)2)2 Complex in CCl4. Transient Species and TD-DFT Calculations Full article

Journal

Journal of Photochemistry and Photobiology A: Chemistry
ISSN: 1010-6030 , E-ISSN: 1873-2666

Output data

Year: 2019, Volume: 381, Article number : 111857, Pages count : 11 DOI: 10.1016/j.jphotochem.2019.111857

Tags

Bis-diisobutyl-dithiophosphinate Ni(II)complex; Intermediate particles; Kinetics; Laser flash photolysis; Photolysis mechanism; Quantum-chemical calculation

Authors

Solovyev Aleksey I. ^1,2 , Mikheylis Aleksandr V. ¹ , Plyusnin Victor F. ^1,2 , Shubin Aleksandr A. ^2,3 , Grivin Vjacheslav P. ¹ , Larionov Stanislav V. ^2,4 , Tkachenko Nikolai V. ⁵ , Lemmetyinen Helge ⁵

Affiliations

1	Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, 630090, Russian Federation
2	Novosibirsk State University, Novosibirsk, 630090, Russian Federation
3	Boreskov Institute of Catalysis SB RAS, Novosibirsk, 630090, Russian Federation
4	Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, 630090, Russian Federation
5	Tampere University, Faculty of Engineering and Natural Sciences, Korkeakoulunkatu 8, Tampere, FI-33720, Finland

Funding (1)

Russian Science Foundation

18-13-00246

Femtosecond spectroscopy and nanosecond laser flash photolysis were used to study the photophysical and photochemical transformations of the bis-diisobutyl-dithiophosphinate Ni(II)complex (Ni(S2P(i-Bu)2)2 = Ni(dtpi)2, where dtpi− ≡ −S2P(i-Bu)2)in CCl4 solutions. The radiation of second harmonic (405 nm)of Ti:Sapphire laser transfers the Ni(dtpi)2 complex to an excited 1LMCT state. Its decay in CCl4 is described by three exponents with time constants 0.58, 2.0 and ˜150 ps. The first process apparently involves the fast transitions from 1LMCT state to 3LMCT due to the intersystem crossing (ISC)and then to lower-lying “hot” 3LF (Ligand Field)state. The second time constant, most likely, corresponds to the vibrational cooling of this “hot” 3LF state. And the third slow process is the transition from 3LF state to ground state (1GS). The quantum yield of photochemical transformation under the 405 irradiation is close to zero, so the study of photochemistry was performed with a nanosecond flash photolysis at 308 nm. In this case an electron transfer from the excited Ni(dtpi)2 complex to a solvent molecule leads to the appearance of primary intermediate, the [ClNi(dtpi)(dtpi[rad])]complex, in which a dtpi[rad] radical is coordinated with a nickel ion via one sulfur atom. In the fast reaction with Ni(dtpi)2, this complex forms a long-lived dimer ClNi(dtpi)(dtpi[rad])[Ni(dtpi)2]. This intermediate for a few hundred microseconds decays in the reaction of recombination with the formation of (dtpi)2 disulphide and unstable ClNi(dtpi)complex. The insoluble NiCl2 salt falled in CCl4 as the sediment due to the reaction of two ClNi(dtpi)complexes. The quantum chemical calculations allowed to determine the geometry of the intermediate complexes arising in the photochemistry of Ni(S2P(i-Bu)2)2 complex. © 2019 Elsevier B.V.

Solovyev A.I. , Mikheylis A.V. , Plyusnin V.F. , Shubin A.A. , Grivin V.P. , Larionov S.V. , Tkachenko N.V. , Lemmetyinen H.
Photochemistry of Dithiophosphinate Ni(S2P(i-Bu)2)2 Complex in CCl4. Transient Species and TD-DFT Calculations
Journal of Photochemistry and Photobiology A: Chemistry. 2019. V.381. 111857 :1-11. DOI: 10.1016/j.jphotochem.2019.111857 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Dec 9, 2018
Accepted:	May 11, 2019
Published online:	May 21, 2019
Published print:	Aug 1, 2019

Web of science:	WOS:000474497600002
Scopus:	2-s2.0-85067953554
Elibrary:	41690136
Chemical Abstracts:	2019:1061741
OpenAlex:	W2945356155

DB	Citing
Scopus	4
Web of science	4
Elibrary	6
OpenAlex	5