Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis | Sciact - CRIS-system of Boreskov Institute of Catalysis

Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2022, Volume: 61, Number: 21, Pages: 8193-8205 Pages count : 13 DOI: 10.1021/acs.inorgchem.2c00487

Tags

Catalysis; Coordination reactions; Fourier transform infrared spectroscopy; Lead compounds; Nuclear magnetic resonance; Nuclear magnetic resonance spectroscopy; Photolysis

Authors

Medvedev Alexander G. ¹ , Grishanov Dmitry A. ^1,2 , Mikhaylov Alexey A. ¹ , Churakov Andrei V. ¹ , Tripol’skaya Tatiana A. ¹ , Ottenbacher Roman V. ³ , Bryliakov Konstantin P. ³ , Shames Alexander I. ⁴ , Lev Ovadia ² , Prikhodchenko Petr V. ¹

Affiliations

1	Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, Russian Federation
2	Casali Center of Applied Chemistry, Hebrew University of Jerusalem, Jerusalem 9190401, Israel
3	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
4	Department of Physics, Ben-Gurion University of Negev, Be'er-Sheva 8410501, Israel

Funding (3)

1	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0009
2	Russian Science Foundation	19-73-10208
3	German Israeli Foundation for Scientific Research and Development	I-1368-307.8/2016

The synthesis, transformation, and application in catalysis of triphenyllead hydroperoxide, the first dioxygen lead complex, are described. Triphenyllead hydroperoxide is characterized by 207Pb nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and single-crystal X-ray diffraction, revealing the first one-dimensional (1D) coordination peroxo polymer. Photolytic isomorphous transformation of Ph3PbOOH yields a mixed hydroxo/superoxo crystalline structure, the first nonalkali superoxo crystalline metal salt, which is stable up to 100 °C. Upon further photolysis, another isomorphous transformation of the superoxide to hydroxide is observed. These are the first single-crystal-to-single-crystal hydroperoxide-to-superoxide and then to hydroxide transformations reported to date. Photolysis of triphenyllead hydroperoxide yields two forms of superoxide-doped crystalline structures that are distinguished by widely different characteristic relaxation times. The use of Ph3PbOOH as an easy-to-handle solid two-electron oxidant for the highly enantioselective epoxidation of olefins is described.

Medvedev A.G. , Grishanov D.A. , Mikhaylov A.A. , Churakov A.V. , Tripol’skaya T.A. , Ottenbacher R.V. , Bryliakov K.P. , Shames A.I. , Lev O. , Prikhodchenko P.V.
Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis
Inorganic Chemistry. 2022. V.61. N21. P.8193-8205. DOI: 10.1021/acs.inorgchem.2c00487 WOS Scopus РИНЦ OpenAlex ANCAN PMID

Submitted:	Feb 12, 2022
Published online:	May 17, 2022
Published print:	May 30, 2022

≡ Web of science:	WOS:000808098800012
≡ Scopus:	2-s2.0-85131269007
≡ Elibrary:	48719752
≡ OpenAlex:	W4280515059
≡ Chemical Abstracts:	2022:1278998
≡ Chemical Abstracts (print):	179:33767
≡ PMID:	35578736

≡ Elibrary	11	Сбор данных от 22.02.2026
≡ Scopus	11	Сбор данных от 22.02.2026
≡ Web of science	11	Сбор данных от 20.02.2026
≡ OpenAlex	13	Сбор данных от 22.02.2026