Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms

2021 ◽  
Author(s):  
Douglas A. Reed ◽  
Taylor J. Hochuli ◽  
Natalia A. Gadjieva ◽  
Shoushou He ◽  
Ren A. Wiscons ◽  
...  
Keyword(s):  
Ligand Coordination ◽  
Coordination Spheres

Steroid imines as chiral ligands. Diastereoselective formation of (1-azadiene)Fe(CO)3 complexes by sterically tuning the ligand coordination spheres

1999 ◽  
Vol 10 (15) ◽  
pp. 2983-2995 ◽  
Author(s):  
Daniel Berger ◽  
Manuela Dubs ◽  
Angela Göbel ◽  
Wolfgang Imhof ◽  
Manuela Kötteritzsch ◽  
...  
Keyword(s):  
Chiral Ligands ◽  
Ligand Coordination ◽  
Coordination Spheres

A new simplifying approach to molecular geometry description: the vectorial bond-valence model

2006 ◽  
Vol 62 (6) ◽  
pp. 1038-1042 ◽  
Author(s):  
Miguel Angel Harvey ◽  
Sergio Baggio ◽  
Ricardo Baggio
Keyword(s):  
Metal Complexes ◽  
Electron Pair ◽  
Molecular Geometry ◽  
Atomic Level ◽  
Bond Valence ◽  
Valence Shell ◽  
Vector Quantity ◽  
Ligand Coordination ◽  
Coordination Spheres ◽  
Bond Valence Model

A method to describe, analyze and even predict the coordination geometries of metal complexes is proposed, based on previous well established concepts such as bond valence and valence-shell electron-pair repulsion (VSEPR). The idea behind the method is the generalization of the scalar bond-valence concept into a vector quantity, the bond-valence vector (BVV), with the innovation that the multidentate ligands are represented by their resultant BVVs. Complex n-ligand coordination spheres (frequently indescribable at the atomic level) reduce to much simpler ones when analyzed in BVV space, with the bonus of a better applicability of the VSEPR predictions. The geometrical implications of the BVV description are analyzed for the cases of n = 2 and 3 (n = number of ligands), and the validity of its predictions, checked for a large number of metal complexes.

Xenon Trioxide Adducts of O-Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3

2018 ◽  
Author(s):  
Katherine Marczenko ◽  
James Goettel ◽  
Gary Schrobilgen
Keyword(s):  
Room Temperature ◽  
Triphenylphosphine Oxide ◽  
Donor Ligands ◽  
Mechanical Shock ◽  
X Ray Diffraction ◽  
X Ray ◽  
Oxygen Coordination ◽  
Xenon Trioxide ◽  
Distorted Octahedra ◽  
Coordination Spheres

Oxygen coordination to the Xe(VI) atom of XeO<sub>3</sub> was observed in its adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO<sub>3</sub>, which detonates when mechanically or thermally shocked, the solid [(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>PO]<sub>2</sub>XeO<sub>3</sub>, [(CH<sub>3</sub>)<sub>2</sub>SO]<sub>3</sub>(XeO<sub>3</sub>)<sub>2</sub>,<sub> </sub>and (C<sub>5</sub>H<sub>5</sub>NO)<sub>3</sub>(XeO<sub>3</sub>)<sub>2</sub> adducts are insensitive to mechanical shock, but undergo rapid deflagration when ignited by a flame. Both [(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>PO]<sub>2</sub>XeO<sub>3 </sub>and (C<sub>5</sub>H<sub>5</sub>NO)<sub>3</sub>(XeO<sub>3</sub>)<sub>2</sub> are air-stable whereas [(CH<sub>3</sub>)<sub>2</sub>SO]<sub>3</sub>(XeO<sub>3</sub>)<sub>2</sub> slowly decomposes over several days and [(CH<sub>3</sub>)<sub>2</sub>CO]<sub>3</sub>XeO<sub>3</sub> undergoes adduct dissociation at room temperature. The xenon coordination sphere of [(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>PO]<sub>2</sub>XeO<sub>3</sub> is a distorted square pyramid which provides the first example of a five-coordinate XeO<sub>3</sub> adduct. The xenon coordination spheres of the remaining adducts are distorted octahedra comprised of three Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO<sub>3</sub>. Quantum-chemical calculations were used to assess the Xe---O adduct bonds, which are predominantly electrostatic σ-hole bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the xenon atoms.

Mechanistic Insights into Fe Catalyzed α-C-H Oxidations of Tertiary Amines

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert
Keyword(s):  
Free Radical ◽  
Catalytic Mechanism ◽  
Catalyst System ◽  
Oxidation Products ◽  
Tertiary Amines ◽  
Catalyst Activation ◽  
Rate Determining Step ◽  
Fe Catalyst ◽  
Ligand Coordination ◽  
Rate Kinetics

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>

scholarly journals Two mixed-ligand coordination polymers based on 2,5-thiophenedicarboxylic acid and flexible N-donor ligands: the protective effect on periodontitis via reducing the release of IL-1β and TNF-α

2020 ◽  
Vol 18 (1) ◽  
pp. 391-398
Author(s):  
Shao-Hsuan Wu ◽  
Jun-Hui Huang
Keyword(s):  
Coordination Polymers ◽  
Gingival Crevicular Fluid ◽  
Mixed Ligand ◽  
Donor Ligands ◽  
X Ray Diffraction ◽  
Functional Studies ◽  
Tnf Α ◽  
Mucosal Cells ◽  
Ligand Coordination ◽  
Crevicular Fluid

AbstractTwo novel mixed-ligand coordination polymers, {[Co(tdc)(btrp)]·0.67DMF}n (1) and {[Zn2(bimb)2(tdc)2]·2H2O}n (2) involving 2,5-thiophenedicarboxylate (H2tdc), and bitopic flexible N-donor ligands, 1,3-bis(1,2,4-triazol-1-yl)propane (btrp) and 1,4-bis((1H-benzo[d]imidazol-1-yl)methyl)benzene (bimb), have been synthesized by the hydrothermal method and characterized via IR, elemental analysis, thermal analysis, and powder X-ray diffraction. The biological functional studies were performed; the treatment activity of the compounds on periodontitis and the specific mechanism was explored. First, the real-time RT-PCR was carried out to determine the inflammatory genes nf-κb and p53 relative expression in periodontal mucosal cells after treating with compounds 1 and 2. Then, the level of the inflammatory cytokine in the gingival crevicular fluid after treating with compounds was also determined by the ELISA detection kit.

Ligand isomerism in Pt(II) complexes – structural aspects

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš
Keyword(s):  
Mixed Ligand ◽  
Bidentate Ligands ◽  
Trans Isomers ◽  
Mean Values ◽  
Bite Angle ◽  
Coordination Spheres ◽  
Structural Aspects

Abstract This review has focused on ligand isomers in Pt(II) complexes. There are a variety of inner coordination spheres about the platinum(II) atom (PtN4, PtN2Cl2, PtP2Cl2, PtPNC2, PtPNCl2, PtP2CBr, PtP2CS), build up by mono- and bidentate ligands. The bidentate ligands create a variety of metallocyclic rings. The L–Pt–L bite angle (mean values) open in the sequence: 73.1° (PNP) < 78.7° (NC2C) < 80.4° (NC2N) < 86.4° (PC2P) < 86.7° (PNNP) < 93.0° (CC3S). There are three types of isomers: ligand, mixed – (ligand + distortion), and mixed – (ligand + cis-trans), isomers, which are rarity.

scholarly journals Structural tuning of heterogeneous molecular catalysts for electrochemical energy conversion

2021 ◽  
Vol 7 (13) ◽  
pp. eabf3989
Author(s):  
Jiong Wang ◽  
Shuo Dou ◽  
Xin Wang
Keyword(s):  
Energy Conversion ◽  
Model Systems ◽  
Structural Variations ◽  
Metal Centers ◽  
Electrochemical Energy Conversion ◽  
Electronic Configurations ◽  
Coordination Spheres ◽  
The Stability ◽  
Molecular Catalysts ◽  
Electrochemical Energy

Heterogeneous molecular catalysts based on transition metal complexes have received increasing attention for their potential application in electrochemical energy conversion. The structural tuning of first and second coordination spheres of complexes provides versatile strategies for optimizing the activities of heterogeneous molecular catalysts and appropriate model systems for investigating the mechanism of structural variations on the activity. In this review, we first discuss the variation of first spheres by tuning ligated atoms; afterward, the structural tuning of second spheres by appending adjacent metal centers, pendant groups, electron withdrawing/donating, and conjugating moieties on the ligands is elaborated. Overall, these structural tuning resulted in different impacts on the geometric and electronic configurations of complexes, and the improved activity is achieved through tuning the stability of chemisorbed reactants and the redox behaviors of immobilized complexes.

scholarly journals Self-Assembled Nanomaterials Based on Complementary Sn(IV) and Zn(II)-Porphyrins, and Their Photocatalytic Degradation for Rhodamine B Dye

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3598
Author(s):  
Nirmal K. Shee ◽  
Hee-Joon Kim
Keyword(s):  
Aqueous Solution ◽  
Visible Light Irradiation ◽  
Rhodamine B ◽  
Self Assembly ◽  
The Self ◽  
Assembly Process ◽  
Absorption Bands ◽  
Ligand Coordination ◽  
Rhodamine B Dye ◽  
Metal Ligand

A series of porphyrin triads (1–6), based on the reaction of trans-dihydroxo-[5,15-bis(3-pyridyl)-10,20-bis(phenyl)porphyrinato]tin(IV) (SnP) with six different phenoxy Zn(II)-porphyrins (ZnLn), was synthesized. The cooperative metal–ligand coordination of 3-pyridyl nitrogens in the SnP with the phenoxy Zn(II)-porphyrins, followed by the self-assembly process, leads to the formation of nanostructures. The red-shifts and remarkable broadening of the absorption bands in the UV–vis spectra for the triads in CHCl3 indicate that nanoaggregates may be produced in the self-assembly process of these triads. The emission intensities of the triads were also significantly reduced due to the aggregation. Microscopic analyses of the nanostructures of the triads reveal differences due to the different substituents on the axial Zn(II)-porphyrin moieties. All these nanomaterials exhibited efficient photocatalytic performances in the degradation of rhodamine B (RhB) dye under visible light irradiation, and the degradation efficiencies of RhB in aqueous solution were observed to be 72~95% within 4 h. In addition, the efficiency of the catalyst was not impaired, showing excellent recyclability even after being applied for the degradation of RhB in up to five cycles.

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