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We present that cationic rings can act as donor ligands thanks to suitably delocalized metal-metal bonds. This could grant parent complexes with the peculiar properties of aromatic rings that are crafted with main group elements. We assembled Pd nuclei into equilateral mono-cationic triangles with unhindered faces. Like their main group element counterparts and despite their positive charge, these noble-metal rings form stable bonding interactions with other cations, such as positively charged silver atoms, to deliver the corresponding tetranuclear dicationic complexes. Through a mix of modeling and experimental techniques we propose that this bonding mode is an original coordination-like one rather than a 4-centre-2-electron bond, which have already been observed in three dimensional aromatics. The present results thus pave the way for the use of suitable metal rings as ligands.
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http://dx.doi.org/10.1039/c7sc03475j | DOI Listing |
Chem Commun (Camb)
December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang 330031, China.
Using temperature modulation, two distinct hydrogen bond organic frameworks HOF-C and HOF-K with different pore sizes were synthesized from the same ligands, tris(4-(4-1,2,4-triazole-4-yl)phenyl)amine. The pore size difference prevents TRZ from entering HOF-K, while allowing TRZ to selectively insert into the larger-pored HOF-C to form HOF-C-TRZ. The donor-acceptor (D-A) structure formed in HOF-C-TRZ enhances its photoelectric response and exhibits exceptional uranium reduction under visible light irradiation.
View Article and Find Full Text PDFDalton Trans
December 2024
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(V) aniline complex supported by an acridane-derived redox active NNN pincer ligand. The reversible binding of aniline to a Ta(V) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N-H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Saarland University, Coordination Chemistry, Campus C 4.1, 66123, Saarbrücken, GERMANY.
We report hitherto elusive side-on η2-bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexa-fluorobenzene) palladium(0) complexes and present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine and tetrahydrofuran complexes reveals that the experimental ligand binding strengths follow the order THF < C6H6 < C6F6 < cyclohexene < pyridine < benzaldehyde < anthraquinone. To understand this surprising order, the complexes' electronic structures were elucidated by nuclear magnetic resonance (NMR), single crystal X-Ray diffraction (sc-XRD), ultraviolet/visible (UV/Vis) electronic absorption, infrared (IR) vibrational, Pd L3-edge X-ray absorption (XAS), and X-ray photoelectron (XP) spectroscopic techniques, complemented by Density Functional Theory (DFT) calculations including energy decomposition (EDA-NOCV) and effective oxidation state (EOS) analyses.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
October 2024
Department of Chemistry and Biochemistry Lamar University, 4400 MLK Blvd Beaumont Texas 77710 USA.
The mercury(II) halide complex [1,3-di--butyl-2,4-bis-(-butyl-amino)-1,3,2λ,4λ-di-aza-diphosphetidine-2,4-diselone-κ ,']di-iodido-mercury(II),-di-methyl-formamide monosolvate, [HgI(CHNPSe)]·CHNO or ()HgI, , containing -[( BuNH)(Se)P(μ-N Bu)P(Se)(NH Bu)] () was synthesized and structurally characterized. The crystal structure of confirms the chelation of chalcogen donors to HgI with a natural bite angle of 112.95 (2)°.
View Article and Find Full Text PDFSmall
December 2024
Department of Chemistry, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India.
Anticipating intramolecular excited-state proton-coupled electron transfer (PCET) process within dinuclear Ir-photocatalytic system via the covalent linkage is seminal, yet challenging. Indeed, the development of various dinuclear complexes is also promising for studying integral photophysics and facilitating applications in catalysis or biology. Herein, this study reports dinuclear [Ir(bis{imidazo-phenanthrolin-2-yl}-hydroquinone)(ppy)] (1) complex by leveraging both ligand-centered redox property and intramolecular H-bonding for exploring dual excited-state proton-transfer assisted PCET process.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!