4,6-Diacetylresorcinol (DAR) serves as precursor for the formation of different hydrazone ligands, which are di-, tetra- or hexa-basic with two symmetrical sets of O(2)N tridentate, O(2)N(2) tetradentate or O(4)N(2) hexadentate chelating sites. The condensation of 4,6-diacetylresorcinol (DAR) with oxalyldihydrazine (ODH), in the molar ratio 1:1 and 1:2, yields the corresponding hydrazone, H(6)L(a) and H(4)L(b), ligands, respectively. The structures of these ligands were elucidated by elemental analyses and IR, mass, (1)H NMR and UV-vis spectra. Reactions of the hydrazone ligands with cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), iron(III) and chromium(III) ions in 1:2 molar ratio afforded the corresponding transition metal complexes. A variety of binuclear transition metal complexes were obtained in its di-, tetra- or hexa-deprotonated forms. The structures of the newly prepared complexes were identified by elemental analyses and IR, UV-vis, mass, (1)H NMR and ESR spectra, as well as, magnetic susceptibility measurements and thermal gravimetric analysis (TGA). The bonding sites are the azomethine and CO oxygen atoms in either keto or enol forms and amino nitrogen atoms, and phenolic oxygen atoms. The metal complexes exhibit different geometrical structures such as tetrahedral and octahedral arrangements.
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http://dx.doi.org/10.1016/j.saa.2007.05.028 | DOI Listing |
Dalton Trans
January 2025
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Phosphole and azaphosphole derivatives with triazole functionalities, [CH{1,2,3-NCCHC(PPh)}] (L1) and [CH{1,2,3-NC(Ph)C(PPh)}] (L2) were synthesized by reacting [(CH)(1,2,3-NC = CH--Br-CH)] and [(-Br-CH)(1,2,3-NC = CHCH)] with BuLi followed by the addition of dichlorophenylphosphine. The reactions of L1 and L2 with an excess of 30% HO afforded phosphole oxides [CH{1,2,3-NCCHC(P(O)Ph)}] (L1O) and [CH{1,2,3-NC(Ph)C(P(O)Ph)}] (L2O) as white crystalline solids. Stoichiometric reactions of L1 and L2 with [Ru(η--cymene)Cl] in CHCl yielded [RuCl(η--cymene)(L1-κ-)] (1) and [RuCl(η--cymene)(L2-κ-)] (2), respectively.
View Article and Find Full Text PDFDalton Trans
January 2025
Institut für Anorganische Chemie, University of Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart, Germany.
A cationic N-heterocyclic phosphenium (NHP) iron tetracarbonyl complex was synthesised from the free cation and its behaviour towards various anionic reactants studied. Reactions with fluoride, chloride, and hydride sources proceeded under attachment of the anion at phosphorus to yield Fe(CO)-complexes of neutral diazaphospholenes, while bromide and iodide reacted under addition of the anion at the metal and decarbonylation to yield NHP iron halides. Reactions with amides and organometallics were unselective.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai 200032, China.
The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization of inert C-H bonds, facilitating the use of nonprecious metal catalysts in demanding transformations. Notably, aerobic C-H carbonylation of methane to acetic acid remains formidable due to the rapid oxidation of methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT to achieve exceptional C2/C1 selectivity through synergistic photoexcitation, methyl radical generation, and carbonylation.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Chemistry, University of Melbourne, Parkville 3010, Victoria, Australia.
A search for switchable molecules has afforded a family of cobalt complexes featuring derivatives of 2-aminophenol: 4,6-di--butyl aminophenol (HL) and 2-anilino-4,6-di--butyl aminophenol (HL). The heteroleptic cobalt complexes incorporate a Metpa ligand (tpa = tris(2-pyridylmethyl)amine; = 0-3), which involves the methylation of the 6-position of the pyridine ring). Eight members of this family have been synthesized and characterized: [Co(HL)(tpa)](BPh) (), [Co(HL)(Metpa)](BPh) (), [Co(L)(Metpa)](BPh) (), [Co(HL)(Metpa)](BPh) (), [Co(L)(Metpa)](BPh) (), [Co(HL)(tpa)] (BPh)(ClO) (), [Co(L)(tpa)](BPh)(ClO) () and [Co(HL)(Metpa)](BPh) (), where the aminophenol-derived ligands are monoanionic in either the open shell radical iminosemiquinonate (L) or the closed shell protonated aminophenolate (HL).
View Article and Find Full Text PDFChem Sci
January 2025
Radioisotope Science and Technology Division, Oak Ridge National Laboratory Oak Ridge TN 37830 USA
Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, CHSiMe (Cp'). The complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4f or 4f 5d, depending on the specific metal.
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