We herein report the first example of an asymmetric ketone hydrogenation using chirally modified derivatives homogeneous iron(II)–cyclopentadienone–tricarbonyl system, known as Casey's catalyst. For synthesis catalysts, one three carbonyl ligands was exchanged for a chiral phosphoramidite. To this end, either oxidative decarbonylation trimethylamine-N-oxide or photolysis applied. Photolysis also used to convert tricarbonyl iron precatalyst (and, analogously, dicarbonyl phosphoramidite...

One for all: A trianionic ligand containing the biologically relevant moieties phenolate and porphyrin was designed synthesized. One-electron oxidation of nickel cobalt complexes these ligands affords an unprecedented highly stable hybrid porphyrinyl–phenoxyl radical bound to metal center. Two-electron leads M2+–(close-shell two-electron oxidized ligand) species.

Lithium batteries are considered as the most promising electricity storage solution to support energy transition but still suffer for cost and sustainable issues related use of metal based electrode materials. Due their reduced environmental fooprint low cost, organic active materials such carbonyl family (quinone, anhydride, diimide) some interesting candidates replace them electrochemical performances in particular redox potential have be increased order become a viable alternative. Here...

Five tetradentate ligands based on the N,N′-bis(2-amino-3,5-di-tert-butylphenyl)-o-phenylenediamine backbone were prepared, with different substituents at positions 4 and 5 (CH3 (3a), p-CH3O-C6H4 (3b), H (3c), Cl (3d), F (3e)). Their reaction a nickel(II) salt in air affords neutral species 4(a-e), which isolated as single crystals. 4(a-e) feature two antiferromagnetically exchange-coupled diiminosemiquinonate moieties, both located peripheral rings, diamidobenzene bridging unit. Oxidation...

The sterically hindered bis(phenol)–dipyrrin ligands HLH3 and PhLH3 were reacted with 1 equiv of copper(II) under ambient conditions to produce the copper radical complexes [Cu(HL)] [Cu(PhL)]. Their X-ray crystal structures show relatively short C–O bond distances (mean 1.287 1.291 Å), reminiscent mixed pyrrolyl–phenoxyl species. Complexes [Cu(PhL)] exhibit rich electronic spectra, an intense near-IR (NIR) band (ε > 6 mM–1 cm–1) at 1346 1321 nm, respectively, assigned a ligand-to-ligand...

Silver-catalyzed tandem acetalization and cycloisomerization reactions were found to lead various furoquinolines, a nitrogen effect was noticed for AgOTf reactivity, since the cyclization mode switched from 6-endo-dig 5-exo-dig; these observations silver imidazolate polymer is proposed as stable catalyst.

Abstract We herein present the first synthesis of 1,1′‐binaphthyl‐2,2′‐bis(sulfuryl)imides (JINGLEs). This new class chiral Brønsted acids was synthesized in one step from corresponding BINOLs and imidobis(sulfuryl chloride). A total six enantiopure 1,1′‐binaphthyl‐2,2′‐bis(sulfuryl)imides, carrying different 3,3′‐substituents, were characterized, inter alia, by X‐ray crystallography.

Abstract Two anilinosalen and a mixed phenol‐anilinosalen ligands involving sterically hindered anilines moieties were synthesized. Their nickel(II) complexes 1 , 2 3 prepared characterized. They could be readily one‐electron oxidized ( E 1/2 =−0.30, −0.26 0.10 V vs. Fc + /Fc, respectively) into anilinyl radicals species [ 1] 2] 3] respectively. The radical are extremely stable isolated as single crystals. X‐ray crystallographic structures reveal that the changes in bond length resulting...

The electron-rich pincer ligand 1 has been synthesized and chelated to manganese. octahedral Mn(iv) bis(diiminosemiquinonate) Mn(v) (diiminobenzoquinone) (diiminosemiquinonate) radicals were structurally characterized.

The tetradentate ligand dppH3, which features a half-porphyrin and two electron-rich phenol moieties, was prepared chelated to manganese. mononuclear Mn(iii)-dipyrrophenolate complex 1 structurally characterized. metal ion lies in square pyramidal environment, the apical position being occupied by methanol molecule. Complex displays reversible oxidation waves at 0.00 V 0.47 vs. Fc+/Fc, are assigned ligand-centered processes. one-electron oxidized species 1+ SbF6- crystallized, showing an...

The cobalt(<sc>ii</sc>) anilinosalen complex [Co^II(L)] was prepared and subsequently oxidized by one electron.

Nickel(II) complexes of (M : L) stoichiometries 1 (1) and 2 (2) were prepared from a polydentate ligand involving diiminosemiquinonate radicals. Both characterized by X-ray diffraction, Vis-NIR EPR spectroscopy as well electrochemistry. Ligand-centered oxidation promotes ejection to give 2.

The sterically hindered bis(2-aminophenyl)dipyrrin ligand H3NL was prepared. X-ray diffraction discloses a bifurcated hydrogen bonding network involving the dipyrrin and one aniline ring. reaction of with equivalent nickel(II) in air produces paramagnetic neutral complex, which absorbs intensively Vis-NIR region. Its electron resonance spectrum displays resonances at g1 = 2.033, g2 2.008, g3 1.962 that are reminiscent an (S 1/2) system having predominant organic radical character. Both...

Abstract Three copper(II) complexes of the ( R , )‐ N ′‐bis(3,5‐di‐ tert ‐butyl‐2‐aminobenzylidene)‐1,2‐diaminocyclohexane ligand, namely [Cu( L)] LH)] + and LH 2 )] 2+ were prepared structurally characterized. In copper ion lies in an octahedral geometry with aniline groups coordinated equatorial positions. anilines are deprotonated (anilido moieties) to almost square‐planar metal ion. Complex displays two oxidation waves at E 1/2 ox, 1 =−0.14 V =0.36 vs. Fc /Fc CH Cl . irreversible wave...

The pincer ligand H 3 L 3N , bis(2‐amino‐3,5‐di‐ tert ‐butylphenyl)amine}, was chelated to Ni II Pd and Pt . Square‐planar complexes of stoichiometry 2:1 (ligand/metal) formed, wherein the coordinates in a bidentate fashion. By X‐ray diffraction we established that each molecule its diiminosemiquinone radical form neutral ( 1 2 respectively). resulting systems are singlet diradical species, with predicted J value range –1062 –1764 cm –1 These diradicals display an intense LLCT transition...

Palladium-catalyzed copper(I)-mediated cross-coupling reaction of 3-methylthio-6-(morpholin-4-yl)-1,2,4,5-tetrazine with a wide range boronic acids and organotin derivatives led to new unsymmetrical aryl- hetaryl-substituted tetrazines in moderate good yields. These results represent the first reactions readily available 3-methylthiotetrazine under Suzuki-like Stille-like conditions could extend scope tetrazine chemistry.

The ability of bis-triazinylpyridine (BTP) molecules to complex lanthanides is well-known in solution and can be judiciously utilized elaborate solid sensing surfaces. This was done by synthesizing a new BTP derivative covalently anchoring it onto gold grafting, its chemical modification the resultant lanthanide complexation were evaluated combining X-ray Photoelectron Spectroscopy (XPS) Polarization Modulation-Infrared Reflection Absorption (PM-IRRAS). detection neodynium europium cations...

The first cobalt-catalysed cycloisomerisation of alkynoic acids is reported, thanks to the design a well-defined diradical cobalt(iii) catalyst, in absence any additives. high efficiency, regioselectivity and chemoselectivity are comparable those noble metal-based systems. unique reactivity might be attributed second coordination sphere effects.

A pyridinium substituted dithienylethene derivative was used for the first time as an efficient photoreducing agent of two different substrates. This reaction exhibits high catalytic yields due to continuous regeneration initial state photochromic molecule.

The bis(di-tert-butyl-aminophenyl)amine ligand H3LN,N,N was reacted with Mn(ii), Co(ii), Fe(iii) and Cu(ii) salts in air. undergoes oxidative transformations, which involve intra intermolecular C-N N-N bond formations. A rare aromatic cleavage leading to a C-O has also been observed.

The N,N ‐bis(2‐amino‐3,5‐di‐ tert ‐butylphenyl)amine pincer ligand was coordinated to copper. Depending on the copper source, a mononuclear complex 1 + or trimer 2 could be isolated and were structurally characterized. Complex consists of two deprotonated iminobenzoquinone ligands Cu(I) center. is trinuclear with (3:3) (M:L) stoichiometry, featuring three‐fold repetition unit made Cu(II) center tridentate radical‐dianion. In , metal ions are bridged by an anilido nitrogen. coordination...

Various 2-benzylsulfanyl-1,3-oxazolines were synthesized and engaged in a copper-promoted palladium-catalyzed cross-coupling reaction with range of organoboryl organostannyl reagents to produce 2-aryl- or 2-hetaryl-substituted oxazolines. Protected unprotected carbohydrate backbones shown be compatible the conditions. This approach opens new versatile access chiral oxazoline structures.