scholarly journals Metal–ligand interactions in complexes of cyclen-based ligands with Bi and Ac

2021 ◽  
Author(s):  
Attila Kovács ◽  
Zoltán Varga
Keyword(s):  
Basis Sets ◽  
Ring Size ◽  
Complex Stability ◽  
Chelating Ligands ◽  
Ligand Interactions ◽  
Bonding Properties ◽  
State Method ◽  
Targeting Vector ◽  
Pendant Arms ◽  
Metal Ligand

AbstractThe structural and bonding properties of Bi and Ac complexes with cyclen-based chelating ligands have been studied using relativistic DFT calculations in conjunction with TZ2P all-electron basis sets. Besides the parent cyclen ligand, the study has covered its extensions with pyridine-type (Lpy), carboxylate (DOTA, DOTPA), picolinate (MeDO2PA) and phosphonate (DOTMP) pendant arms. The effect of the cyclen ring size has been probed by increasing it from [12]aneN4 to [16]aneN4. Additional extensions in the DOTA complexes included the H2O ligand at the 9th coordination site as well as the p-SCN-Bn substituent (a popular linker to the targeting vector). The study focuses on the complex stability, the nature of bonding and the differences between Ac and Bi in the complexes. The metal–ligand interactions have been analysed by the Extended Transition State method combined with Natural Orbitals of Chemical Valence theory and Quantum Theory of Atoms in Molecules models.

scholarly journals Multiwavelets Applied to Metal-Ligand Interactions: Energies Free from Basis Set Errors

2021 ◽  
Author(s):  
Anders Brakestad ◽  
Peter Wind ◽  
Stig Rune Jensen ◽  
Luca Frediani ◽  
Kathrin Hopmann
Keyword(s):  
Transition Metal ◽  
Basis Set ◽  
Basis Sets ◽  
Electronic Interaction ◽  
Promising Alternative ◽  
Ligand Interactions ◽  
Counterpoise Corrections ◽  
Solvent Molecules ◽  
Catalyzed Reactions ◽  
Metal Ligand

The following article will be submitted to the Journal of Chemical Physics. It is thus not a peer-reviewed manuscript. After it is hopefully accepted for publication, it will be found (in revised form) at https://aip.scitation.org/journal/jcp<div><br></div><div>Transition metal-catalyzed reactions invariably include steps, where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision Multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands such as H2, CO, olefins and solvent molecules. By comparing our Multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ, when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors. <br></div>

scholarly journals Multiwavelets Applied to Metal-Ligand Interactions: Energies Free from Basis Set Errors

2021 ◽  
Author(s):  
Anders Brakestad ◽  
Peter Wind ◽  
Stig Rune Jensen ◽  
Luca Frediani ◽  
Kathrin Hopmann
Keyword(s):  
Transition Metal ◽  
Basis Set ◽  
Basis Sets ◽  
Electronic Interaction ◽  
Promising Alternative ◽  
Ligand Interactions ◽  
Counterpoise Corrections ◽  
Solvent Molecules ◽  
Catalyzed Reactions ◽  
Metal Ligand

The following article will be submitted to the Journal of Chemical Physics. It is thus not a peer-reviewed manuscript. After it is hopefully accepted for publication, it will be found (in revised form) at https://aip.scitation.org/journal/jcp<div><br></div><div>Transition metal-catalyzed reactions invariably include steps, where ligands associate or dissociate. In order to obtain reliable energies for such reactions, sufficiently large basis sets need to be employed. In this paper, we have used high-precision Multiwavelet calculations to compute the metal-ligand association energies for 27 transition metal complexes with common ligands such as H2, CO, olefins and solvent molecules. By comparing our Multiwavelet results to a variety of frequently used Gaussian-type basis sets, we show that counterpoise corrections, which are widely employed to correct for basis set superposition errors, often lead to underbinding. Additionally, counterpoise corrections are difficult to employ, when the association step also involves a chemical transformation. Multiwavelets, which can be conveniently applied to all types of reactions, provide a promising alternative for computing electronic interaction energies free from any basis set errors. <br></div>

Magnetic and Spectroscopic Studies on Copper(II) and Chromium(III) Complexes With Sulfur Chelating Ligands

1986 ◽  
Vol 39 (4) ◽  
pp. 605 ◽  
Author(s):  
AC Fabretti ◽  
C Preti ◽  
L Tassi ◽  
G Tosi ◽  
P Zannini
Keyword(s):  
Magnetic Moment ◽  
Spectroscopic Studies ◽  
Chelating Ligands ◽  
Conductivity Measurements ◽  
Bonding Parameters ◽  
Ligand Interactions ◽  
Different Temperatures ◽  
Metal Ligand

A number of complexes of chromium(III) and copper(II) with heterocyclic dithiocarbamate ligands is reported. The newly prepared compounds are characterized on the basis of near- i.r . and far- i.r . spectroscopy, electronic and e.p.r . spectra, conductivity measurements and magnetic moment studies at different temperatures. The dithio ligands exhibit bidentate behaviour acting as S,S′-donors in all the complexes. The chromium(III) compounds have g values in the 1.991-1.999 range and nephelauxetic parameters indicative of an appreciable metal- ligand covalency. The e.p.r . data of the copper(II) derivatives provide parameters typical of sulfur coordination in planar CuS4 chromophores ; the α bonding parameters are indicative of strongly covalent metal- ligand interactions.

scholarly journals Different manifestations of enhanced π-acceptor ligation at every redox level of [Os(9-OP)L2]n, n = 2+, +, 0, − (9-OP− = 9-oxidophenalenone and L = bpy or pap)

2016 ◽  
Vol 45 (45) ◽  
pp. 18241-18251 ◽  
Author(s):  
Arijit Singha Hazari ◽  
Alexa Paretzki ◽  
Jan Fiedler ◽  
Stanislav Zalis ◽  
Wolfgang Kaim ◽  
...  
Keyword(s):  
Donor And Acceptor ◽  
Ligand Interactions ◽  
Redox Level ◽  
Metal Ligand

Enhanced metal–ligand and ligand–ligand interactions are promoted in an osmium complex with non-innocent donor and acceptor ligands.

scholarly journals Reversible Assembly of Terpyridine Incorporated Norbornene-Based Polymer via a Ring-Opening Metathesis Polymerization and Its Self-Healing Property

Polymers ◽  
2018 ◽  
Vol 10 (10) ◽  
pp. 1173 ◽  
Author(s):  
Jookyeong Lee ◽  
Hwi Moon ◽  
Keewook Paeng ◽  
Changsik Song
Keyword(s):  
Ring Opening ◽  
Transition Metal Ions ◽  
Self Healing ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Ligand Interactions ◽  
Healing Agent ◽  
Healing Property ◽  
External Stimuli ◽  
Metal Ligand

We induced a terpyridine moiety into a norbornene-based polymer to demonstrate its self-healing property, without an external stimulus, such as light, heat, or healing agent, using metal–ligand interactions. We synthesized terpyridine incorporated norbornene-based polymers using a ring-opening metathesis polymerization. The sol state of diluted polymer solutions was converted into supramolecular assembled gels, through the addition of transition metal ions (Ni2+, Co2+, Fe2+, and Zn2+). In particular, a supramolecular complex gel with Zn2+, which is a metal with a lower binding affinity, demonstrated fast self-healing properties, without any additional external stimuli, and its mechanical properties were completely recovered.

Metal–ligand interactions in Fe(II)-dioxime complexes

2008 ◽  
Vol 867 (1-3) ◽  
pp. 1-4 ◽  
Author(s):  
Balázs Krámos ◽  
Attila Kovács
Keyword(s):  
Ligand Interactions ◽  
Metal Ligand
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