The pressure-induced transformation of plane-square complex nickel(II) bis(N,N-diethyldithiocarbamate) between its soft dithiocarbamate (form I) and thioureide (form II) mesomeres is coupled to the interchange of anagostic Ni⋅⋅⋅H-C interactions from methylene to the methyl group, respectively. At 1.23 GPa, the clearly visible giant anomalous compressibility of the crystal reveals a potential-energy difference of 5.4 kJ mol between the two complex forms. The structural and spectroscopic results, which are supported by quantum-mechanical calculations, connect this solid-state phase transition with the mesomeric transition, and this is accompanied by the conformational transformation of anagostic Ni⋅⋅⋅H-C rearrangement and formation of the charge-assisted S ⋅⋅⋅H-C bond under pressure.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.202201235 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Probing the nature of intramolecular (sp)C-H⋯Cu(I) interactions in organo thione copper(I) cages.
Dalton Trans
January 2025
Organometallics and Materials Chemistry Lab, Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana, 502285, India.
The assessment of copper(I) and hydrogen interactions is challenging and should be approached with caution. In this paper, we report an assessment of multiple copper(I) and hydrogen interactions in two unique copper(I) thione cages. Copper(I) -heterocyclic thione cages [{Cu(-Br)(-L1)}] (1) and [{Cu(-I)(-L1)}] (2) were synthesized and characterized with proximity enforced Cu⋯H interactions.
View Article and Find Full Text PDFChiral Biaryl N-Heterocyclic Carbene-Palladium Catalysts with Anagostic C-H···Pd Interaction for Enantioselective Desymmetric C-N Cross-Coupling.
Org Lett
November 2024
Department of Chemistry, Gwangju Institute of Science and Technology, 123 Cheomdan-gwagi-ro Buk-gu, Gwangju 61005, Republic of Korea.
Novel chiral biaryl imidazo[1,5-]pyridine carbene-palladium complexes (ImPy-Pd) featuring an anagostic C-H···Pd interaction and a C5-aryl substituent have been developed and successfully applied to the Pd-catalyzed enantioselective desymmetric C-N cross-coupling of malonamide derivatives, providing chiral 3,4-dihydroquinoline-2-ones with quaternary stereocenters in high yields (≤99%) and enantioselectivities (≤97:3 er). The chiral catalyst exerts stereocontrol by restricting the rotation of substituents around the metal center through anagostic interactions with sterically bulky substituents.
View Article and Find Full Text PDFElectron Density and Molecular Orbital Analyses of the Nature of Bonding in the η-CCH Agostic Rhodium Complexes Preceding the C-C and C-H Bond Cleavages.
Molecules
October 2024
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 7610001, Israel.
In our recent work, we revisited C-H and C-C bond activation in rhodium (I) complexes of pincer ligands PCP, PCN, PCO, POCOP, and SCS. Our findings indicated that an η-CCH agostic intermediate acts as a common precursor to both C-C and C-H bond activation in these systems. We explore the electronic structure and bonding nature of these precleavage complexes using electron density and molecular orbital analyses.
View Article and Find Full Text PDFDesigning a Phenalenyl-Based Dinuclear Ni(II) Complex: An Electrocatalyst with Two Single Ni Sites for the Oxygen Evolution Reaction (OER).
Inorg Chem
May 2024
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Rajasthan 342030, India.
A new dinuclear Ni(II) complex , [Ni(dtbh-PLY)], is synthesized from 9-(2-(3,6-di--butyl-2-hydroxybenzylidene)hydrazineyl)-1-phenalen-1-one, dtbh-PLYH ligand, and structurally characterized by various analytical tools including the single-crystal X-ray diffraction (SCXRD) technique. In the solid state, both Ni(II) metal centers in complex exist in a distorted square planar geometry and display the presence of rare Ni···H-C anagostic interactions to form a one-dimensional (1-D) linear motif in the supramolecular array. Complex is further stabilized in the solid state by π-π-stacking interactions between the highly delocalized phenalenyl rings.
View Article and Find Full Text PDFSelective Gold Precipitation by a Tertiary Diamide Driven by Thermodynamic Control.
Inorg Chem
May 2024
EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, United Kingdom.
The simple diamide ligand was previously shown to selectively precipitate gold from acidic solutions typical of e-waste leach streams, with precipitation of gallium, iron, tin, and platinum possible under more forcing conditions. Herein, we report direct competition experiments to afford the order of selectivity. Thermal analysis indicates that the gold-, gallium-, and iron-containing precipitates present as the most thermodynamically stable structures at room temperature, while the tin-containing structure does not.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!