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Influence of Noncovalent Interaction on the Nucleophilicity and Electrophilicity of Metal Centers in [M(SCNEt)] (M = Ni, Pd, Pt).
J Phys Chem A
December 2024
College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024, China.
A systematic theoretical study was performed on the electrophilic and nucleophilic properties of Group 10 square-planar metal compounds [M(SCNEt)] (M = Ni , Pd , and Pt ) and their complexes. The nucleophilic metal center and coordinated sulfur atom in [M(SCNEt)] facilitate the formation of metal-involving and conventional noncovalent bonds. The presence a heavier metal center results in a more negative electrostatic potential and a larger nucleophilicity, which in turn leads to the formation of stronger metal-involving noncovalent bonds than those formed by a lighter metal center.
View Article and Find Full Text PDFRevisiting Isomerism in Square Planar Palladium NHC Complexes with NacAc Chelators.
Inorg Chem
October 2024
Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117453, Republic of Singapore.
Quantifying the donor ability of bidentate ligands in inorganic chemistry is not straightforward, and the Huynh electronic parameter for chelators (HEP2) presents a rare solution to the task. Aiming to extend the ligand scope in this work, the soundness and practicality of HEP2 was further scrutinized with seven stereoelectronically diverse β-ketiminato ("NacAc") chelators using palladium complexes of the type [PdBr(Pr-bimy)(NacAc)] (Pr-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene). Notably, the unsymmetrical nature of this κ-, ligand family allowed for an intriguing exploration into isomerism in the square planar Pd products, which depends on the -aryl - and -substituents based on experimental and theoretical findings.
View Article and Find Full Text PDFHerein, the first example of a homoleptic Ag complex stabilized by a monodentate N-donor ligand is presented. Na[SO] oxidizes the linear Ag complex, Na[Ag(succ)] (1), to form a square planar argentate(iii) ion, [Ag(succ)], which crystallizes with a polymeric chain-structure, M[Ag(succ)] (2), when treated with alkali metal sulfate MSO (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(HO)Ag][Ag(succ)] (2), forms in the absence of K/Rb/Cs ion.
View Article and Find Full Text PDFSpectroscopic, anti-cancer, anti-bacterial and theoretical studies of new bivalent Schiff base complexes derived from 4-bromo-2,6-dichloroaniline.
Heliyon
September 2024
Department of Chemistry, College of Science, Tikrit University, Tikrit, Iraq.
In this paper, four new mono-nuclear Ni(II), Pd(II), Pt(II) and Zn(II) complexes were prepared by using a bi-dentate Schiff base ligand, ()-2-(((4-bromo-2,6-dichlorophenyl)imino)methyl)-5-chlorophenol (), with bivalent ions in a methanol and distil water mixture as solvent in presence of NaOH as base. The structures of the prepared compounds were characterized by spectroscopic techniques (IR and H NMR), CHN analysis, and molar conductivity. The M(II) (Ni, Pd and Pt) ions are four-coordinated by a bi-dentate NO donor ligand, forming square planar geometry, whereas the Zn(II) is coordinated as a tetrahedral geometry.
View Article and Find Full Text PDFNi(II) and Pd(II) complexes of a new redox-active pentadentate azo-appended 2-aminophenol ligand: Pd(II)-assisted intraligand cyclization forms a phenoxazinyl ring.
Dalton Trans
August 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
Square planar complexes of Ni(II) and Pd(II) of a new redox-active pentadentate azo-appended 2-aminophenol ligand (HL = ,'-bis(2-hydroxy-3,5-di--butylphenyl)-2,2'-diamino--azobenzene) in three accessible redox levels [amidophenolate(2-), semiquinonate(1-) π radical, and quinone(0)] were synthesized. The coordinated HL(3-) ligand provides four donor sites [two N(iminophenolates), an N'(azo), and an O(phenolate)], while the phenolic OH group remains free in the three complexes. Cyclic voltammetry on complex [Ni(L)] 1 and its corresponding Pd(II) analogue [Pd(L)] 2 in CHCl displayed three redox responses (two oxidative at = 0.
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