The atom economical borrowing hydrogen methodology enables the use of alcohols as alkylating agents for selective C-C bond formation. A bifunctional 2-(2-pyridyl-2-ol)-1,10-phenanthroline (phenpy-OH) based Ru(ii) complex (2) was found to be a highly efficient catalyst for the one-pot β-alkylation of secondary alcohols with primary alcohols and double alkylation of cyclopentanol with different primary alcohols. Exploiting the metal-ligand cooperativity in complex 2, several aromatic, aliphatic and heteroatom substituted alcohols were selectively cross-coupled in high yields using significantly low catalyst loading (0.1 mol%). An outer-sphere mechanism is proposed for this system as exogenous PPh has no significant effect on the rate of the reaction. Notably, this is a rare one-pot strategy for β-alkylation of secondary alcohols using a bifunctional Ru(ii)-complex. Moreover, this atom-economical methodology displayed the highest cumulative turn over frequency (TOF) among all the reported transition metal complexes in cross coupling of alcohols.
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http://dx.doi.org/10.1039/c6ob02010k | DOI Listing |
Inorg Chem
January 2025
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A and 2B Raja S. C. Mullick Road, Kolkata 700032, India.
The incorporation of a selenoimidazolium-based chalcogen bond (ChB) donor into a bis-heteroleptic Ru(II) complex (Ru-Se) has been designed for the first time to explore its anion-sensing properties and understand its selectivity to specific classes of anions. Photophysical studies demonstrate the receptor's selectivity toward phosphates, while H NMR displays its ability to recognize both I and HPO among the different halides and oxoanions through ChB interaction in CHCN and dimethyl sulfoxide- solvents, respectively. Additionally, microscopic studies such as DLS and TEM reveal that the selective turn-on sensing of HPO and HPO compared to I is driven by supramolecular aggregation behavior.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department for Chemistry, Technical University of Denmark (DTU), 2800 Kongens Lyngby, Denmark.
A new Ru(II) complex featuring a novel amino-di(N-heterocyclic carbene) CNC pincer ligand, CNC-RuCl(CO) (Ru-1), has been developed and characterised in depth. Ru-1 forms an efficient and durable catalytic formic acid dehydrogenation system in combination with the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM PO(OEt)).
View Article and Find Full Text PDFChemistry
January 2025
Heidelberg University, Anorganisch-Chemisches Institut, Im Neuenheimer Feld 276, 69120, Heidelberg, GERMANY.
Targeting Ru(III) and Ru(I) η2-alkyne species, 2,2'-(iPr2E)2-substituted diphenylacetylenes (1-E, E = P, As) were em-ployed for the pre-paration of [ECCE]-coordinated ruthenium com-plexes. The re-actions between 1-E and cis-(MeCN)2(COD)RuCl2 led to the required Ru(II) starting materials cis-[ECCE]RuCl2(MeCN) (3-E). Upon oxi-dation of 3-E with PhICl2, the Ru(III) target com-plexes [ECCE]RuCl3 (7-E) were detectable for E = P and E = As, but only the arsa-deriva-tive 7-As was obtained in a pure form, namely via oxi-da-tion of cis-[AsCCAs]RuCl2(THT) (THT = tetrahydrothiophene).
View Article and Find Full Text PDFSensors (Basel)
December 2024
Chemical Optosensors & Applied Photochemistry Group (GSOLFA), Department of Organic Chemistry, Faculty of Chemistry, Complutense University of Madrid, 28040 Madrid, Spain.
Water conductivity sensing relies universally on electrical measurements, which are subject to corrosion of the electrodes and subsequent signal drift in prolonged in situ uses. Furthermore, they cannot provide contactless sensing or remote readout. To this end, a novel device for water conductivity monitoring has been developed by employing a microenvironment-sensitive ruthenium complex, [Ru(2,2'-bipyridine-4,4'-disulfonato)], embedded into a quaternary ammonium functionalized cross-linked polymer support.
View Article and Find Full Text PDFMol Pharm
January 2025
School of Pharmacy, Jiangsu Province Key Laboratory for Inflammation and Molecular Drug Target, Nantong University, Nantong 226001, Jiangsu Province, China.
Photodynamic therapy (PDT) is increasingly regarded as an attractive approach for cancer treatment due to its advantages of low invasiveness, minimal side effects, and high efficiency. Here, two novel Ru(II) complexes , were designed and synthesized by coordinating phenanthroline and biquinoline ligands with Ru(II) center, and their chemo-photodynamic therapy and immunotherapy were explored. Both and exhibited significant phototoxicity against A549 and 4T1 tumor cells type-I/-II PDT.
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