Semistable Half‐Sandwich Cp*Co(II)(P‐X) (X=N, O) Complexes: Synthesis, Characterization and Electrochemical Properties DOI
Xuewen Zhuang,

Xingshang Weng,

Xiaochun Zhang

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(40)

Published: Oct. 1, 2024

Abstract Three Cp*Co(II)(P−X) (X=N, O) complexes were synthesized using cyclopentadienyl anionic and [P N]/[P O] bidentate ligands. Crystallographic analysis revealed five‐coordinate, 17‐electron unsaturated structures with low‐spin d⁷ Co(II) configurations. Electrochemical studies showed reversible Co(II)/Co(III) redox couples an irreversible Co(II)/Co(I) process of Cp*Co(II)(P−O) complexes, while complex Cp*Co(II)(P−N) exhibited due to the pyridine imine ligand. Oxidation AgBF 4 produced stable Co(III) confirmed by crystallographic data NMR data. These exhibit significant electrochemical properties stability, indicating potential for catalytic organic molecule binding applications.

Language: Английский

Flash Communication: Ligand Centered Cooperative O–H Bond Splitting by a Mo(CO)5(phosphine) Complex DOI Creative Commons

Sotirios Pavlidis,

Josh Abbenseth

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

The synthesis and reactivity of a molybdenum carbonyl complex ligated by geometrically constrained phosphorus trisamide are reported. Reaction with potassium tert-butoxide or methanol triggers ligand-centered substrate activation, leading to planarization the phosphine donor ligand. P–O bond formation, decarbonylation, insertion center into ligand P–N result in formation tetracarbonyl complexes rigid N,P-chelate ligands.

Language: Английский

Citations

0
Meta-Xylene-Based Diamines with Protected Benzyl Sites: Potential NCN Pincer Ligands with Tunable Steric Profiles DOI Creative Commons

Tamina Kirsch,

Toren Hynes,

Jason D. Masuda

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(6), P. 1331 - 1331

Published: March 16, 2025

Bulky NCN aryl-diamides featuring methyl groups in the benzyl positions were synthesized with aim of creating a new class meta-xylene-based trianionic pincer ligands where common decomposition pathway metal complexes via C-H activation is prevented. Sterically demanding substituents on furthermore provide steric protection centre and can help prevent dimerization complexes. While double deprotonation formation dilithium salt was straightforward, difficulties encountered when attempting to deprotonate ipso-CH proton central aryl ring yield ligands. This stands contrast related without benzylic positions. Experimental theoretical investigations led conclusion that challenges third are likely caused by an interplay increased electron density at nitrogen atoms hindrance. Both effects originate introduction positions, which make targeted less accessible. These results further insight into impact both electronic properties ligands, may find utility coordination chemistry applications metalation be achieved direct rather than requiring triple deprotonation.

Language: Английский

Citations

0
Comparative Study of the Structures and Reactivities of Cationic Nickel and Palladium Complexes with a Bismuth-Bisphosphine (PBiP) Ligand DOI Creative Commons
Kent S. Gates,

Yuka Aoyama,

Hang Cao

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Language: Английский

Citations

0
Geometrically Constrained Bismuth Compounds DOI

Tamina Kirsch,

Saurabh S. Chitnis

Structure and bonding, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Ir(I)–Bi(III) Donor–Acceptor Adducts Stabilized by Dispersion Interactions between the Metal Pincer Ligands and Their Possible Self-Assembly Forming Molecular 1D Semiconductors DOI
Zdeněk Chval

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(27), P. 12417 - 12425

Published: June 26, 2024

Structure, stability, and electronic properties of the bimetallic {[IrI(terpy)(Me)]-[BiIIINNN]}n monomeric, oligomeric, polymeric structures (n = 1–3 ∞; terpy terpyridine; Me methyl; BiNNN bismuth triamide) their derivatives (designated as (Bi·Ir)n structures) were studied theoretically by DFT cluster periodic calculations. Stable Bi·Ir adducts (monomers) formed with short Bi–Ir bonds (<2.7 Å) Gibbs free binding energies larger than 20 kcal/mol for all systems. The substitution pincer ligands Ir(I) Bi(III) complexes electron-donating (NH2) electron-withdrawing (NO2, F, CF3) groups, respectively, enhanced Ir → Bi charge transfer, substantially stabilizing monomers. monomers from unsubstituted can be considered dispersion stabilized adducts, they may form spontaneously layered oligomers/polymers semiconducting properties. self-assembly into is hindered bulkier protecting groups on complex, such tBu SiMe3.

Language: Английский

Citations

3
Precatalyst Evolution in PBiP-Pd Complexes for Electrocatalytic Proton Reduction DOI Creative Commons
Hang Cao,

Yuka Aoyama,

Kristen Mast

et al.

Published: May 8, 2024

Main-group metals as supporting ligands for transition offer potential bimetallic synergistic effects. We investigated a bismuth-palladium system utilizing PBiP pincer ligand (BiPdCl) precatalysts electrocatalytic proton reduction with thiophenol. Rinse tests revealed the formation of surface-bound active species, likely comprised Pd-based heterogenous materials. NMR and UV-visible spectroscopic studies unveiled that in diluted solutions polar coordinating solvents, chloride trans to bismuthane readily dissociates, affording solvent-coordinated species (BiPdsolvent) predominant solution species. Following thiol– solvent exchange, an equilibrium mixture solvent-bound thiolate complex (BiPdS) forms. The crystal structures BiPdS acetonitrile-coordinated model (BiPdAcN) shows thermodynamic influence ligand. Structural analysis, corroborated by computational investigations, suggests BiPdsolvent is primarily ligand-based than Pd-centered, hinting at Bi(III)–Pd(0) oxidation states rather Bi(I)–Pd(II) suggested Lewis structure BiPdsolvent. electron-rich Pd electron-poor Bi centers explain its electrochemical decomposition similar other Pd(0) Our findings shed light on electronic properties reactivities studied Bi–Pd compounds, offering example ambiguous within this system.

Language: Английский

Citations

1
Coordination chemistry of ligands bearing heavy group 14 and 15 elements: Comparative analysis of their influence on transition metal chemistry DOI

Yeong Jun Son,

Dongyoung Kim, Jae Wan Park

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 526, P. 216317 - 216317

Published: Dec. 3, 2024

Language: Английский

Citations

1
Semistable Half‐Sandwich Cp*Co(II)(P‐X) (X=N, O) Complexes: Synthesis, Characterization and Electrochemical Properties DOI
Xuewen Zhuang,

Xingshang Weng,

Xiaochun Zhang

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(40)

Published: Oct. 1, 2024

Abstract Three Cp*Co(II)(P−X) (X=N, O) complexes were synthesized using cyclopentadienyl anionic and [P N]/[P O] bidentate ligands. Crystallographic analysis revealed five‐coordinate, 17‐electron unsaturated structures with low‐spin d⁷ Co(II) configurations. Electrochemical studies showed reversible Co(II)/Co(III) redox couples an irreversible Co(II)/Co(I) process of Cp*Co(II)(P−O) complexes, while complex Cp*Co(II)(P−N) exhibited due to the pyridine imine ligand. Oxidation AgBF 4 produced stable Co(III) confirmed by crystallographic data NMR data. These exhibit significant electrochemical properties stability, indicating potential for catalytic organic molecule binding applications.

Language: Английский

Citations

0