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Mas Balleste, RubenAuthorHermosilla Minguez, LauraAuthorSieiro CAuthor

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O-O Bond activation in H2O2 and (CH3) 3C-OOH mediated by [Ni(cyclam)(CH3CN)2] (ClO4)2: Different mechanisms to form the same Ni(iii) product?

Publicated to:DALTON TRANSACTIONS. 40 (26): 6868-6876 - 2011-07-14 40(26), DOI: 10.1039/c0dt01605e

Authors: Solans-Monfort X; Fierro J; Hermosilla L; Sieiro C; Sodupe M; Mas-Ballesté R

Affiliations

CSIC - Instituto de Catálisis y Petroleoquímica (ICP) - Author
Universidad Autónoma de Madrid - Author
Universitat Autònoma de Barcelona - Author

Abstract

Reaction of [NiII(cyclam)(CH3CN)2] (ClO4)2 (1) with tert-butylhydroperoxide (TBHP) or H 2O2, in acidic media results in a formation of [Ni III(cyclam)(CH3CN)2]3+ species (2), the nature of which is characterized by UV-vis, EPR and XPS. The formation rate of 2 is much higher when H2O2 is used as oxidant. In absence of acid, TBHP reacts with 1 generating the same Ni(iii) species but, in contrast, no reaction is observed between H2O2 and 1. Addition of cis-stilbene as an oxidable substrate quenches the formation of Ni(iii) for reaction with H2O2 only. Overall, these observations reveal a different reaction mechanism when reacting H 2O2 with 1 than when reacting the same metal complex with TBHP, despite the fact that the final product is the same. The proposed pathways arising from these observations consist in a homolytic O-O cleavage for the reaction of 1 with TBHP in CH3CN, but a proton assisted heterolysis for the O-O activation in H2O2. Density functional calculations (B3LYP and OPBE) on the thermodynamic feasibility of the two reaction processes support the proposed mechanisms, since the O-O homolysis is strongly disfavored when H2O2 is used as reactant. © 2011 The Royal Society of Chemistry.

Keywords

Astronomia / físicaBiotecnologíaChemistry, inorganic & nuclearCiências agrárias iCiências ambientaisCiências biológicas iCiências biológicas iiEngenharias iEngenharias iiEngenharias iiiEngenharias ivEnsinoFarmaciaGeneral medicineInorganic chemistryInterdisciplinarMateriaisMedicina iiOdontologíaQuímica

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal DALTON TRANSACTIONS due to its progression and the good impact it has achieved in recent years, according to the agency WoS (JCR), it has become a reference in its field. In the year of publication of the work, 2011, it was in position 7/44, thus managing to position itself as a Q1 (Primer Cuartil), in the category Chemistry, Inorganic & Nuclear.

From a relative perspective, and based on the normalized impact indicator calculated from the Field Citation Ratio (FCR) of the Dimensions source, it yields a value of: 1.9, which indicates that, compared to works in the same discipline and in the same year of publication, it ranks as a work cited above average. (source consulted: Dimensions Jun 2025)

Specifically, and according to different indexing agencies, this work has accumulated citations as of 2025-06-13, the following number of citations:

  • WoS: 12
  • Scopus: 13
  • Europe PMC: 7
  • OpenCitations: 15

Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2025-06-13:

  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 22 (PlumX).

Leadership analysis of institutional authors

There is a significant leadership presence as some of the institution’s authors appear as the first or last signer, detailed as follows: Last Author (Mas-Balleste R).