Stepwise transformation of a redox-active tetradentate ONNO ligand in the coordination sphere of tin(IV)

Stepwise transformation of a redox-active tetradentate ONNO ligand in the coordination sphere of tin(IV) Full article

Journal

Dalton Transactions
ISSN: 1477-9226

Output data

Year: 2025, Volume: 54, Number: 18, Pages: 7281-7293 Pages count : 13 DOI: 10.1039/d5dt00430f

Authors

Meshcheryakova Irina N ¹ , Cherkasov Anton V ¹ , Arsenyev Maxim V ¹ , Aysin Rinat R ² , Belikov Aleksey A ¹ , Bogomyakov Artem S ³ , Protasenko Natalya A ¹ , Kocherova Tatiana N ¹ , Baryshnikova Svetlana V ¹ , Piskunov Alexandr V ¹

Affiliations

1	G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Street, 603137 Nizhny Novgorod, Russia. mina@iomc.ras.ru.
2	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, str. 1, Moscow, 119334, Russia.
3	International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia.

New diorganotin(IV) complexes based on a redox-active tetradentate ONNO ligand, namely N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine (LH4), were synthesized. A methodology for the stepwise oxidation of tin(IV)-ONNO derivatives with a stoichiometric amount of p-benzoquinone was developed. This allowed the preparation of tin(IV) complexes containing the ligand in the tetraanionic doubly deprotonated form, in the dianionic state, and a controlled intraligand cyclization to be carried out. It has been found that the diorganotin(IV) compounds with the dianionic form of the ONNO ligand have a ground singlet spin state, but an increase in temperature leads to partial populating of the triplet state and a transition from the diamagnetic form of these complexes to the paramagnetic biradical ones. The UV-vis-NIR spectrum of L2−SnPh2 shows an intense absorption band in the range of 600–1400 nm, corresponding to the intraligand charge transfer (ILCT). The coordination ability of the solvent strongly influences the position of this solvatochromic band. Cyclic voltammetry revealed that this compound undergoes two sequential reversible single-electron oxidations and two sequential reversible single-electron reductions. This cyclic voltammetry remains unchanged even after 100 cycles have been performed.

Meshcheryakova I.N. , Cherkasov A.V. , Arsenyev M.V. , Aysin R.R. , Belikov A.A. , Bogomyakov A.S. , Protasenko N.A. , Kocherova T.N. , Baryshnikova S.V. , Piskunov A.V.
Stepwise transformation of a redox-active tetradentate ONNO ligand in the coordination sphere of tin(IV)
Dalton Transactions. 2025. V.54. N18. P.7281-7293. DOI: 10.1039/d5dt00430f WOS Scopus OpenAlex

Submitted:	Feb 21, 2025
Accepted:	Mar 26, 2025
Published online:	Mar 27, 2025
Published print:	May 14, 2025

Web of science:	WOS:001461916000001
Scopus:	2-s2.0-105002416218
OpenAlex:	W4408926206

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OpenAlex	2
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