Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry

Abstract

Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[β-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV–Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2.

Proton Affinity in the Chemistry of Beta-Octamolybdate: HPLC-ICP-AES, NMR and Structural Studies

“…One of the central complexes in this chemistry is (Bu 4 N) 4 [β-Mo 8 O 26 ] ( Scheme 1 ), which is a standard precursor of all reactions in organic media, leading to a huge number of materials with different properties [ 46 , 47 , 48 , 49 ]. Our ongoing research focuses on the use of the coordination chemistry of the [β-Mo 8 O 26 ] 4− anion in the study of silver chemistry in non-aqueous solutions [ 50 , 51 , 52 ]. Karoui and Ritchie used (Bu 4 N) 4 [β-Mo 8 O 26 ] in the microwave-assisted synthesis of tris(alkoxo)molybdovanadates [V 3 Mo 3 O 16 (O 3 -R)] 2− (R = C 5 H 8 OH or C 4 H 6 NH 2 ) by the reaction between [β-Mo 8 O 24 ] 4− , [H 3 V 10 O 28 ] 3− and pentaerythritol or tris(hydroxymethyl)aminomethane [ 53 ].…”

Effects of Bis(imino)acenaphthene (Bian)-Derived Ligands on the Cytotoxicity, DNA Interactions, and Redox Activity of Palladium(II) Bipyridine Complexes

“…As a result, metal complexes with Bian ligands are typically characterized by rich redox chemistry incliding the redox isomerism (reversible intramolecular electron transfer), − which enables their use for various applications. For example, metal complexes with Bian ligands can be used in multielectron activation processes of small molecules and catalytic reactions based on redox transformations. ,− In particular, square-planar Pd­(II) complexes of the [Pd II X 1 X 2 (Bian)] type, where X 1 and X 2 are Cl, CH 3 , OH, etc., have been investigated as catalysts for olefin polymerization reactions (Brookhart catalysts). − …”

Gold(i) complexes with redox active BIAN and MIAN ligands: synthesis, structure and electrochemistry

“…This property has been widely exploited in various research groups for design of numerous catalytic processes. 1,[6][7][8][9][10][11][12][13][14][15] On the other hand, the redox-active nature of BIANs and their metal complexes can play a key role in ensuring the biological activity of such compounds. The number of studies on this subject is, however, still limited.…”

“…In another study, BIAN-supported NHC Au(I) complexes ([IPr(BIAN)AuOAc] and [IPr(BIAN)AuCl]) have been studied as antimicrobial and antitumoral agents. [23][24][25] In Au(I) complexes with diimines such as 2,2 0 -bipyridine, 1,10-phenanthroline and their substituted derivatives [26][27][28] an antichelate effect was found, which is expressed in the asymmetric coordination of the chelating ligand to the heavy d 10 ions. This is facilitated by the presence of an auxiliary ligand with strong s-donor properties (for example, phosphines).…”