Metal-to-ligand charge transfer in polarized metal L-edge X-ray absorption of Ni and Cu complexes

2004 ◽  
Vol 136 (1-2) ◽  
pp. 67-75 ◽  
Author(s):  
Takaki Hatsui ◽  
Nobuhiro Kosugi
Keyword(s):  
Charge Transfer ◽  
X Ray ◽  
Ligand Charge Transfer ◽  
X Ray Absorption ◽  
Cu Complexes

scholarly journals Probing CuI in homogeneous catalysis using high-energy-resolution fluorescence-detected X-ray absorption spectroscopy

2015 ◽  
Vol 51 (48) ◽  
pp. 9864-9867 ◽  
Author(s):  
Richard C. Walroth ◽  
Jacob W. H. Uebler ◽  
Kyle M. Lancaster
Keyword(s):  
Charge Transfer ◽  
Homogeneous Catalysis ◽  
Energy Resolution ◽  
Catalytic Reaction ◽  
High Energy ◽  
High Energy Resolution ◽  
X Ray ◽  
Ligand Charge Transfer ◽  
X Ray Absorption ◽  
Absorption Features

CuI X-ray absorption features are assigned as metal-to-ligand charge transfer bands. These features facilitate species identification in catalytic reaction mixtures.

scholarly journals Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 981
Author(s):  
Mason D. Hart ◽  
John J. Meyers ◽  
Zachary A. Wood ◽  
Toshinori Nakakita ◽  
Jason C. Applegate ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Coordination Chemistry ◽  
Single Crystal ◽  
13C Nmr ◽  
Quantitative Assessment ◽  
X Ray ◽  
New Class ◽  
Linear Relationships ◽  
Ligand Charge Transfer ◽  
Donor Characteristics

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3.

The charge transfer effect in Pd compounds (II): evidence from the L3 X-ray absorption near edge structure spectroscopy

2004 ◽  
Vol 59 (6) ◽  
pp. 901-904 ◽  
Author(s):  
Zhenlin Liu ◽  
Katsumi Handa ◽  
Kazuki Kaibuchi ◽  
Yoichi Tanaka ◽  
Jun Kawai
Keyword(s):  
Charge Transfer ◽  
Transfer Effect ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

Observation of charge transfer cascades in α-Fe2O3/IrOxphotoanodes by operando X-ray absorption spectroscopy

2017 ◽  
Vol 19 (8) ◽  
pp. 5715-5720 ◽  
Author(s):  
Alessandro Minguzzi ◽  
Alberto Naldoni ◽  
Ottavio Lugaresi ◽  
Elisabetta Achilli ◽  
Francesco D'Acapito ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Absorption Spectroscopy ◽  
X Ray ◽  
X Ray Absorption

In Situ X-Ray Diffraction and In Situ X-Ray Absorption Spectroscopy for Investigation of Intercalation Batteries: Application to the Alkaline H+/γ-MnO2 system.

1990 ◽  
Vol 210 ◽  
Author(s):  
C. Lévy-Clèment ◽  
C. Mondoloni ◽  
C. Godart ◽  
R. Cortès
Keyword(s):  
Charge Transfer ◽  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Crystallographic Structure ◽  
X Ray Diffraction ◽  
Alkaline Batteries ◽  
X Ray ◽  
In Situ Techniques ◽  
X Ray Absorption

AbstractThis paper presents applications of in situ X-ray diffraction and absorption techniques to the study of H+/MnO2 alkaline batteries. The two complementary in situ techniques are described. Investigation of the electrochemical insertion and deinsertion of H+ has been made through its influence on the evolution of the crystallographic structure of γ-MnO2, while investigation of the transfer of e has been undertaken through the variation of the oxidation state of the manganese during the discharging and charging process of a battery. New insights in the understanding of the mechanisms of proton insertion and charge transfer into γ-MnO2 are discussed.

Charge density studies of 3dmetal (Ni/Cu) complexes with a non-innocent ligand

2017 ◽  
Vol 73 (4) ◽  
pp. 634-642 ◽  
Author(s):  
Yu-Chun Chuang ◽  
Chou-Fu Sheu ◽  
Gene-Hsiang Lee ◽  
Yu-Sheng Chen ◽  
Yu Wang
Keyword(s):  
High Resolution ◽  
Charge Density ◽  
Reduced Form ◽  
X Ray Diffraction ◽  
X Ray ◽  
Oxidation Reduction ◽  
Square Planar ◽  
Square Planar Complexes ◽  
X Ray Absorption ◽  
Cu Complexes

High-resolution X-ray diffraction experiments and atom-specific X-ray absorption experiments are applied to investigate a series of square planar complexes with the non-innocent ligand of maleonitriledithiolate (mnt), [S2C2(CN)2]z−, containingM—S bonds. Four complexes of (PyH)z[M(mnt)2]z−, whereM= Ni or Cu,z= 2 or 1 and PyH+= C5NH6+, were studied in order to clarify whether such one-electron oxidation–reduction, [M(mnt)2]2−/[M(mnt)2]1−, is taking place at the metal or the ligand site. Combining the techniques of metalK-,L-edge and SK-edge X-ray absorption spectroscopy with high-resolution X-ray charge density studies, it is unambiguously demonstrated that the electron redox reaction is ligand based and metal based for Ni and Cu pairs, respectively. The bonding characters in terms of topological properties associated with the bond critical points are compared between the oxidized form [ML]−and the reduced form [ML]2−. In the case of Ni complexes, the formal oxidation state of Ni remains as Ni2+and each mnt ligand carries a 2− charge in [Ni(mnt)2]2−, but only one of the ligands is formally oxidized in [Ni(mnt)2]1−. In contrast, in the case of Cu complexes, the mnt remains as 2− in both complexes, but the formal oxidation states of the metal are Cu2+and Cu3+. Bond characterizations andd-orbital populations will be presented. The complementary results of XAS, XRD and DFT calculations will be discussed. The conclusion on the redox reactions in these complexes can be firmly established.

scholarly journals Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

2008 ◽  
Vol 10 (38) ◽  
pp. 5882 ◽  
Author(s):  
Sébastien Bonhommeau ◽  
Niko Pontius ◽  
Saioa Cobo ◽  
Lionel Salmon ◽  
Frank M. F. de Groot ◽  
...  
Keyword(s):  
Thin Films ◽  
Charge Transfer ◽  
Prussian Blue ◽  
Absorption Spectroscopy ◽  
Metal Charge ◽  
X Ray ◽  
Prussian Blue Analogues ◽  
X Ray Absorption ◽  
Metal Charge Transfer
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