scholarly journals Electronic structure and reactivity of nickel(i) pincer complexes: their aerobic transformation to peroxo species and site selective C–H oxygenation

2016 ◽  
Vol 7 (6) ◽  
pp. 3533-3542 ◽  
Author(s):  
Christoph A. Rettenmeier ◽  
Hubert Wadepohl ◽  
Lutz H. Gade
Keyword(s):  
Electronic Structure ◽  
Pincer Complexes ◽  
Peroxo Complex ◽  
Peroxo Complexes ◽  
Site Selective

The dinuclear nickel peroxo complexes undergo autoxidation giving a cyclic alkoxo or peroxo complex in the presence or absence of O2, respectively.

scholarly journals Electronic structure of Schiff-base peroxo{2,2′-[1,2-phenylenebis(nitrilomethanylylidene)]bis(6-methoxyphenolato)}titanium(IV) monohydrate: a possible model structure of the reaction center for the theoretical study of hemoglobin

IUCrJ ◽  
2021 ◽  
Vol 8 (2) ◽  
pp. 295-304
Author(s):  
Júlia Adamko Kožíšková ◽  
Martin Breza ◽  
Marián Valko ◽  
Peter Herich ◽  
Lukáš Bučinský ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Theoretical Study ◽  
Central Atom ◽  
Topological Analysis ◽  
Titanium Atom ◽  
Model Structure ◽  
Peroxo Complex ◽  
Charge Density Distribution ◽  
Apical Position

An extensive characterization of [Ti(C22H18N2O6)]·H2O was performed by topological analysis according to Bader's quantum theory of atoms in molecules (QTAIM) from the experimentally (multipole model) and theoretically (DFT) determined electron density. To the best of our knowledge, this study is the first example of an experimental electronic structure of a coordination compound in which a peroxo anion is bonded to a 3d central atom. The titanium coordination polyhedron could be described as a deformed tetrahedral pyramid if the midpoint of the peroxide O—O bond (side-on mode) is considered to be in the quasi-apical position. According to the multipole model (MM) results, the titanium atom has a positive QTAIM charge of 2.05 e− which does not correspond to the formal Ti (IV) oxidation state. On the other hand, the peroxo oxygen atoms O(1) and O(2) have MM QTAIM charges of −0.27 and −0.12, respectively. This asymmetric charge density distribution on the peroxo oxygens is in agreement with the distorted orientation of the O2 moiety with respect to the titanium atom. Despite the fact that the overall MM charge of the O2 moiety is more remote from the formal −2 charge than from neutral O2, the O—O distance remains close to that in the peroxo O2 2− anion. In the case of DFT results, the titanium atom charge is also found to be close to +2, the O2 x− moiety charge is around −1, the optimized O—O distance is shorter by only ca 0.04 Å than the experimental value of 1.5005 (16) Å, and the DFT d-populations on titanium are found to be lower than the experimental MM value. This study is the first experimental electronic structure of a transition metal peroxo complex.

Ligand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(i) PNP complexes: reactivity insights from electronic structure

2016 ◽  
Vol 45 (24) ◽  
pp. 9774-9785 ◽  
Author(s):  
Kyounghoon Lee ◽  
Haochuan Wei ◽  
Anastasia V. Blake ◽  
Courtney M. Donahue ◽  
Jason M. Keith ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Small Molecule ◽  
Pincer Complexes ◽  
Dft Studies

Ligand K-edge XAS and DFT studies of ligand variations in Rh(i) pincer complexes and correlations to small molecule reactivity.

scholarly journals Geometric and electronic structure and reactivity of a mononuclear ‘side-on’ nickel(iii)–peroxo complex

2009 ◽  
Vol 1 (7) ◽  
pp. 568-572 ◽  
Author(s):  
Jaeheung Cho ◽  
Ritimukta Sarangi ◽  
Jamespandi Annaraj ◽  
Sung Yeon Kim ◽  
Minoru Kubo ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Peroxo Complex

Pyrrolyl-based pincer complexes of iron – Synthesis and electronic structure

Polyhedron ◽  
2018 ◽  
Vol 143 ◽  
pp. 83-93 ◽  
Author(s):  
Nico Ehrlich ◽  
Dirk Baabe ◽  
Matthias Freytag ◽  
Peter G. Jones ◽  
Marc D. Walter
Keyword(s):  
Electronic Structure ◽  
Pincer Complexes

scholarly journals Site-selective electronic structure of pure and doped Ca2O3Fe3S2

2018 ◽  
Vol 98 (4) ◽  
Author(s):  
L. Craco ◽  
B. Freelon ◽  
A. M. Alafailakawi ◽  
B. Karki ◽  
S. Leoni
Keyword(s):  
Electronic Structure ◽  
Site Selective
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