Cationic ruthenium(II) complexes enabled efficient redox-neutral annulations of alkynes with readily available oximes. The catalytic dehydrative C-H/N-O bond functionalization proved to be broadly applicable and was shown to proceed through a reversible cyclometalation.
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http://dx.doi.org/10.1021/jo301768b | DOI Listing |
Chem Asian J
December 2024
National Institute of Pharmaceutical Education and Research, Medicinal Chemistry, Sector 67, 160062, S. A. S. Nagar, INDIA.
Ru(II)-Catalyzed "On Water" direct aryl C(sp2)-H amidation of 2-arylbenzo[d]-thiazole/oxazole with acyl azide is reported under silver-free condition. Deuterium scrambling experiments suggested reversible C-H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C-H amidation except for PhCl in which case, however, inferior yield (31%) was obtained.
View Article and Find Full Text PDFDalton Trans
December 2024
Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council of Italy (CNR), Via Piero Gobetti 101, 40129 Bologna, Italy.
The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy)(azab-py)], where dtbbpy = 4,4'-di--butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)] (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)(ppy)], where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)(naft-py)] (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan.
Oligomerization of monomeric molybdate and tungstate oxyanions in the presence of organometallic cations produces a group of organometallic-polyoxometalate clusters, which have diverse structures based on cubane-like {MO} units resembling the structure of oxide surfaces. This work investigated the oligomerization of [MoO] and [WO] oxyanions in aqueous solutions in the presence of {Ru(CH)} as the organometallic structure-directing agents. The reactions produced a mixture of several species, and fractional crystallization by adjusting crystallization temperature and molar ratios of Ru:Mo or Ru:W allowed the isolation of seven types of (benzene)ruthenium-polyoxometalate complexes: [{Ru(CH)}MoO] (), [{Ru(CH)(OH)}HMoO][MoO] (), [{Ru(CH)}HMoO] (), [{Ru(CH)}WO] (), Na[{Ru(CH)}HWO] (), [{Ru(CH)}HWO] (), and [{Ru(CH)(OH)}WO][{Ru(CH)}{Ru(CH)(OH)}HWO] ().
View Article and Find Full Text PDFInt J Biol Macromol
December 2024
Department of Chemical Sciences, University of Naples Federico II, Complesso Univ. di Monte Sant'Angelo, via Cinthia, 26, 80126 Naples, Italy. Electronic address:
The charge of paddlewheel diruthenium complexes has a major role in defining their interaction with proteins: negatively charged complexes bind proteins non-covalently, while cationic complexes form adducts where the Ru core binds to Asp side chains at the equatorial sites, or to the main chain carbonyl groups or the side chains of His, Arg or Lys residues at the axial sites. Here we study the interactions of the neutral compound [Ru(D-p-FPhF)(OCCH)(OCO)]·3HO (D-p-FPhF = N,N'-bis(4-fluorophenyl)formamidinate), a very rare example of a paddlewheel diruthenium compound with three different equatorial ligands, with the model protein bovine pancreatic ribonuclease (RNase A) by means of UV-visible absorption spectroscopy, circular dichroism (CD), electrospray ionization mass spectrometry (ESI-MS) and X-ray crystallography. It is the first attempt to investigate the binding of a neutral diruthenium compound to a protein.
View Article and Find Full Text PDFChemistry
November 2024
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, 518060, China.
Numerous metallo-supramolecules with well-defined sizes and shapes have been successfully constructed via the strong coordination interaction between terpyridine (TPY) moieties and ruthenium cations. However, the pseudo-octahedral geometry of
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