期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 41, 页码 9737-9746出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201901758
关键词
C-C bond cleavage; electrochemistry; mechanism; redox non-innocence; ruthenium
资金
- Science and Engineering Research Board (SERB, New Delhi)
- IIT Bombay
- DAAD (Germany)/ UGC (India) under the IGP program
- J.C. Bose fellowship (SERB)
In the recent years, there has been an emerging research interest in the domain of C-C bond-cleavage reactions. The present contribution deals with the redox-mediated dioxygen activation and C-C bond cleavage in a diruthenium complex [(acac)(2)Ru-II(mu-L1)Ru-II(acac)(2)], 1 (acac=acetylacetonate) incorporating 2,2 '-pyridil (L1) as the bridging ligand. The above process leads to a C-C-cleaved monomeric product [(acac)(2)Ru-III(pic(-))], 2 (pic(-)=piconilate). Intriguingly, similar diastereomeric complexes [(acac)(2)Ru-II(mu-L2)Ru-II(acac)(2)], meso (Delta Lambda): 3a and rac (Delta Delta/Lambda Lambda): 3b, involving an analogous diimine bridge (L2=N1,N2-diphenyl-1,2-di(pyridin-2-yl)ethane-1,2-diimine), were stable towards such oxidative transformations. Electrochemical and spectroelectrochemical studies, in combination, establish the potential non-innocent feature of the 2,2 '-Pyridil (L1) and its derivative (L2) both in oxidation and reduction processes. Additionally, theoretical calculations have been employed to verify the redox states and their behavior. Furthermore, transition state (TS) calculations at the M06L/6-31G*/LANL2DZ level of theory together with detailed kinetic studies outline a putative mechanism for the selective transformation of 1 -> 2 involving the formation of an intermediate bearing peroxide linkage to complex 1.
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