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A new class of half‐sandwich (η6‐p‐cymene) ruthenium(II) complexes supported by 2‐aminofluorene derivatives [Ru(η6‐p‐cymene)(Cl)(L)] (L = 2‐(((9H‐fluoren‐2‐yl)imino)methyl)phenol (L1), 2‐(((9H‐fluoren‐2‐yl)imino)methyl)‐3‐methoxyphenol (L2), 1‐(((9H‐fluoren‐2‐yl)imino)methyl)naphthalene‐2‐ol (L3) and N‐((1H‐pyrrol‐2‐yl)methylene)‐9H‐fluorene‐2‐amin...
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The intention of this survey is to highlight the innovative electrolyte combination of 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) with tertiary nitrogen bases in electro‐organic synthesis. This easy applicable and promising mixture is not yet well established in electro‐organic synthesis but expands the various possibilities in the latter. Combinatio...
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... The bond lengths between Ru-N and Ru-Cl are 2.159(4) and 2.4005-2.4304 Å, respectively, as reported previously for Ru(II) p-cymene complexes [40]. However, Ru-C (p-cymene) bond lengths are in the range of 2.160-2.208 ...
A new complex (Ru(η6-p-cymene)(5-ASA)Cl2) (1) where 5-ASA is 5-aminosalicylic acid has been prepared by reacting the ruthenium arene precursors ((η6-arene)Ru(μ-Cl)Cl)2, with the 5-ASA ligands in a 1:1 ratio. Full characterization of complex 1 was accomplished by elemental analysis, IR, and TGA following the structure obtained from a single-crystal X-ray pattern. The structural analysis revealed that complex 1 shows a “piano-stool” geometry with Ru-C (2.160(5)- 2.208(5)Å), Ru-N (2.159(4) Å) distances, which is similar to equivalents sister complex. Density functional theory (DFT) was used to calculate the significant molecular orbital energy levels, binding energies, bond angles, bond lengths, and spectral data (FTIR, NMR, and UV–VIS) of complex 1, consistent with the experimental results. The IR and UV–VIS spectra of complex 1 were computed using all of the methods and choose the most appropriate way to discuss. Hirshfeld surface analysis was also executed to understand the role of weak interactions such as H⋯H, C⋯H, C-H⋯π, and vdW interactions, which play a significant role in the crystal environment’s stability. Moreover, the luminescence results at room temperature show that complex 1 gives a more intense emission band positioned at 465 nm upon excitation at 330 nm makes it a suitable candidate for the building of photoluminescent material.
Chemodivergent synthesis by transition metal catalysts is a straightforward and sustainable approach to achieving valuable organic compounds. Especially, the chemodivergent dehydrogenative couplings of alcohols with organic motifs to develop various saturated and unsaturated compounds are highly environmentally benign due to the reduced waste generation. In this concept review, we presented the 3d transition metal (Mn, Fe, Co, and Ni)‐catalyzed chemodivergent synthesis of imines and amines, saturated and unsaturated carbonyl/alcohol compounds, saturated and unsaturated nitriles, N‐heterocycles, and N‐/C‐alkylated indoles. The discussed reaction commanded two or three different products with high chemoselectivity by changing specific reaction parameters, but keeping the catalyst unchanged. Generally, the acceptorless dehydrogenative coupling (ADC) provides unsaturated moieties, whereas the borrowing‐hydrogen (BH) process results in saturated compounds.
Direct oxidative coupling of alcohols and amines is an environmental-benign and atomic-economy approach for imine synthesis. We disclosed that UiO-66 framework successfully confined Ru to single-atom scale with assistance of oxophilic Zn²⁺ promoter. This [email protected] catalyst showed a highest TOF of 78 h⁻¹ among all Ru catalysts in literature and attained >99% yield to benzylideneaniline in the model reaction in an O2 atmosphere at a low temperature without alkaline additives. In addition, this catalyst demonstrated satisfying gram-scale imine synthesis, wide substrate scope and stable reusability. Kinetic investigations and in situ characterizations allowed getting insights to active sites, amphoteric carrier and reaction mechanism. Dynamic interactions between Ru and Zn based on their ratios induced electron-deficient Ru⁰ active sites promoted by oxophilic Zn²⁺ species. Hence, primary alcohols can be efficiently converted to the corresponding aldehydes using molecular O2, i.e., the rate-determining step. Besides, Zr⁴⁺-O²⁻ pairs on UiO-66 provided adequate acidic-basic sites for the tandem catalysis.
The utility and selectivity of the newly synthesized dinuclear arene Ru(II) complex were demonstrated towards the synthesis of imines from coupling of alcohols and amines in the aerobic condition. Analytical and various spectral methods have been used to establish the unprecedented formation of the new thiolato‐bridged dinuclear ruthenium complex. The molecular structure of the titled complex was evidenced with aid of X‐ray crystallographic technique. A wide range of imines were obtained in good‐to‐excellent yields up to 98% and water as the by‐product through an acceptorless dehydrogenative coupling of alcohols with amines. The catalytic reaction operated a concise atom economical without any oxidant with 1 mol% of the catalyst load. Further, the role of base, solvent and catalyst loading of the coupling reaction has been investigated. A plausible mechanism has been described and was found to proceed via the formation of an aldehyde intermediate. Short synthesis of antibacterial drug N‐(salicylidene)‐2‐hydroxyaniline illustrated the utility of the present protocol.
