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The Role of Ligands in Oxidative Addition Chemistry of Low-Valent Main Group Derivatives: Not Only Stabilization but Also Activation Full article

Journal Organometallics
ISSN: 1520-6041 , E-ISSN: 0276-7333
Output data Year: 2023, Volume: 42, Number: 18, Pages: 2541-2548 Pages count : 8 DOI: 10.1021/acs.organomet.2c00607
Authors Shangin Pavel G. 1 , Akyeva Anna Ya. 1 , Vakhrusheva Daria M. 1 , Minyaev Mikhail E. 1 , Mankaev Badma N. 2 , Balycheva Victoriya A. 1 , Lalov Andrey V. 1 , Egorov Mikhail P. 1 , Karlov Sergey S. 2 , Syroeshkin Mikhail A. 1
Affiliations
1 Zelinsky Institute of Organic Chemistry RAS, Leninsky prospect 47, Moscow 119991, Russia
2 Lomonosov Moscow State University, B-234 Leninskie Gory, Moscow 119991, Russia

Abstract: At present, the use of low-valent derivatives of the main group elements, including metallylenes, etc., in catalysis as an alternative to transition metals is widely discussed. The high reactivity of these compounds often requires their stabilization by using electron-pair donor ligands. The influence of the latter on oxidative addition reactions is usually not considered. In this work, to the best of our knowledge for the first time, using the example of the oxidative insertion of Lappert’s germylene into PhSSPh in the presence of N, S, P, and O donor ligands, we show that the ligands significantly increase the reaction rate. This can be associated with an increase in the level of the germylene highest occupied molecular orbital under the influence of a donor. Qualitatively, the obtained values of the reaction rate constants correlate well with the germylene oxidation potentials in the presence of ligands or ligand oxidation potentials.
Cite: Shangin P.G. , Akyeva A.Y. , Vakhrusheva D.M. , Minyaev M.E. , Mankaev B.N. , Balycheva V.A. , Lalov A.V. , Egorov M.P. , Karlov S.S. , Syroeshkin M.A.
The Role of Ligands in Oxidative Addition Chemistry of Low-Valent Main Group Derivatives: Not Only Stabilization but Also Activation
Organometallics. 2023. V.42. N18. P.2541-2548. DOI: 10.1021/acs.organomet.2c00607 WOS Scopus OpenAlex
Identifiers:
Web of science: WOS:000937099100001
Scopus: 2-s2.0-85149028815
OpenAlex: W4321612345
Citing:
DB Citing
OpenAlex 15
Web of science 14
Scopus 14
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