Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

N-C bond formation between two anilines coordinated to a ruthenium center in cis-form affording a 3,5-cyclohexadiene-1,2-diimine moiety.

ABSTRACT: Ruthenium complexes containing two anilines or its derivatives, cis-[Ru^II(NH₂C₆H₅)₂(bpy)₂]²⁺ ([1]²⁺) and cis-[Ru^II(NH₂C₆H₄(4-CH₃))₂(bpy)₂]²⁺ ([2]²⁺), were oxidized by four molar equivalents of (NH₄)₄[Ce^IV(SO₄)₄]·2H₂O to give N ¹-phenylcyclohexa-3,5-diene-1,2-diimineruthenium(ii) complexes, cis-[Ru^II(NHC₆H₄ NC₆H₅)(bpy)₂]²⁺ ([4]²⁺) and cis-[Ru^II(NHC₆H₃(4-CH₃)NC₆H₄(4-CH₃))(bpy)₂]²⁺ ([5]²⁺), respectively, through an N-C bond formation between two aniline ligands cis-coordinated to the ruthenium center.

SUBMITTER: Tomioka N

PROVIDER: S-EPMC9043462 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

N-C bond formation between two anilines coordinated to a ruthenium center in cis-form affording a 3,5-cyclohexadiene-1,2-diimine moiety.

Tomioka Nozomi N Nanbu Shinkoh S Misawa-Suzuki Tomoyo T Nagao Hirotaka H

RSC advances 20211115 58

Ruthenium complexes containing two anilines or its derivatives, cis-[RuII(NH2C6H5)2(bpy)2]2+ ([1]2+) and cis-[RuII(NH2C6H4(4-CH3))2(bpy)2]2+ ([2]2+), were oxidized by four molar equivalents of (NH4)4[CeIV(SO4)4]·2H2O to give N ...[more]

PMID: 35494383

Similar Datasets

Nitrone Cycloadditions of 1,2-Cyclohexadiene.

Project description:We report the first 1,3-dipolar cycloadditions of 1,2-cyclohexadiene, a rarely exploited strained allene. 1,2-Cyclohexadiene is generated in situ under mild conditions and trapped with nitrones to give isoxazolidine products in synthetically useful yields. The reactions occur regioselectively and exhibit a notable endo preference, thus resulting in the controlled formation of two new bonds and two stereogenic centers. DFT calculations of stepwise and concerted reaction pathways are used to rationalize the observed selectivities. Moreover, the strategic manipulation of nitrone cycloadducts demonstrates the utility of this methodology for the assembly of compounds bearing multiple heterocyclic units. These studies showcase the exploitation of a traditionally avoided reactive intermediate in chemical synthesis.

| S-EPMC4899974 | biostudies-literature

Silyl Tosylate Precursors to Cyclohexyne, 1,2-Cyclohexadiene, and 1,2-Cycloheptadiene.

Project description:Transient strained cyclic intermediates have become valuable intermediates in modern synthetic chemistry. Although silyl triflate precursors to strained intermediates are most often employed, the instability of some silyl triflates warrants the development of alternative precursors. We report the syntheses of silyl tosylate precursors to cyclohexyne, 1,2-cyclohexadiene, and 1,2-cycloheptadiene. The resultant strained intermediates undergo trapping in situ to give cycloaddition products. Additionally, the results of competition experiments between silyl triflates and silyl tosylates are reported.

| S-EPMC7329329 | biostudies-literature

Interception of 1,2-cyclohexadiene with TEMPO radical.

Project description:Transient strained cyclic intermediates, such as strained cyclic allenes, are useful building blocks for the synthesis of structurally and stereochemically complex scaffolds. Trappings of strained cyclic allenes are thought to occur primarily through either two or one electron processes. Regarding the latter, diradical intermediates have been invoked in (2 + 2) cycloadditions and (3 + 2) nitrone cycloadditions. The present study questions if a monoradical pathway could exist for strained cyclic allene reactivity, as examined in the reaction of 1,2-cyclohexadiene and TEMPO radical. Our findings suggest the viability of this monoradical pathway.

| S-EPMC8699062 | biostudies-literature

Synthesis of eunicellane-type bicycles embedding a 1,3-cyclohexadiene moiety.

Project description:The first synthesis of diterpenoid eunicellane skeletons incorporating a 1,3-cyclohexadiene moiety is presented. Key step is a low-valent titanium-induced pinacol cyclization that proved to be perfectly diastereoselective. Determination of the relative configuration of the diol was aided by the conversion to the diastereomer by oxidation and reduction. Conformational analysis of some of the resulting diols obtained under McMurry conditions was complicated by the presence of several conformers of similar energy. The pinacol coupling appears to start at the ketone, as indicated by the selective reduction of non-cyclizing cyclohexane systems that were synthesized from limonene oxide. The title compounds and their synthetic precursors are prone to aromatization on contact with air oxygen. Attempted synthesis of cyclohexene-containing eunicellane bicycles by elimination of water from tertiary alkynyl carbinols afforded novel allene systems. Our study may be of help towards the total synthesis of solenopodin or klysimplexin derivatives.

| S-EPMC6176824 | biostudies-literature

Concise Approach to Cyclohexyne and 1,2-Cyclohexadiene Precursors.

Project description:Silyl triflate precursors to cyclic alkynes and allenes serve as valuable synthetic building blocks. We report a concise and scalable synthetic approach to prepare the silyl triflate precursors to cyclohexyne and 1,2-cyclohexadiene. The strategy involves a retro-Brook rearrangement of an easily accessible cyclohexanone derivative, followed by triflation protocols. This simple, yet controlled, method should enable the further study of strained alkynes and allenes in chemical synthesis.

| S-EPMC6935045 | biostudies-literature

Surface-Bound Ruthenium Diimine Organometallic Complexes: Excited-State Properties.

Project description:Ruthenium complexes of the general formula [Ru(CO)(H)(L2)(L'2)][PF6] (L2 = trans-2PPh3, L' = η2-4,4'-dicarboxybipyridine (1); L2 =trans-2Ph2PCH2CH2COOH, L'2 = bipyridine (2); L2 = Ph2PCHCHPPh2, L' = η2-5-amino-1,10-phenanthroline (3); L2 = trans-2PPh3, L'2 = η2-4-carboxaldehyde-4'-methylbipyridine (4)) have been shown to have longer emission lifetimes and higher quantum yields in solution compared with more symmetrical molecules such as [Ru(bpy)3][Cl]2. Compound 4 is obtained as a mixture with the corresponding acetal, 4'. These less symmetrical complexes have been covalently immobilized on the surface of silica polyamine composites, and their photophysical properties have been studied. The surface-bound complexes have been characterized by solid-state CPMAS 13C, 31P, and 29Si NMR, UV-vis, and FT-IR spectroscopies. Excited-state lifetime studies revealed that, in general, the lifetimes of the immobilized complexes are 1.4 to 8 times longer than in solution and are dependent on particle size (300-500 μm versus 10-20 nm average diameter silica gels), polymer structure (linear poly(allylamine) versus branched poly(ethylenimine)), and the type of surface tether. One exception to this trend is the previously reported complex [Ru(bpy)2(5-amino-1,10-phenanthroline)][PF6]2 (5), where only a slight increase in lifetime is observed. Only minor changes in emission wavelength are observed for all the complexes. This opens up the possibility for enhanced heterogeneous electron transfer in photocatalytic reactions.

| S-EPMC4036732 | biostudies-literature

Dual Behavior of Iodine Species in Condensation of Anilines and Vinyl Ethers Affording 2-Methylquinolines.

Project description:A metal-free, mild and efficient method for the synthesis of 2-methylquinolines was successfully developed by condensation of anilines with vinyl ethers in the presence of catalytic amount of iodine. Modification of both pyridine and benzene moieties was easily achieved by changing only the vinyl ether and aniline. In this reaction, the iodine species was revealed to show dual behavior; molecular iodine serves as an oxidant, while its reduced form, hydrogen iodide, activates the vinyl ether. The redox reaction between these iodine species enables the use of a catalytic amount of iodine in this synthetic method.

| S-EPMC6272995 | biostudies-literature

Light-triggered modulation of cellular electrical activity by ruthenium diimine nanoswitches.

Project description:Ruthenium diimine complexes have previously been used to facilitate light-activated electron transfer in the study of redox metalloproteins. Excitation at 488 nm leads to a photoexcited state, in which the complex can either accept or donate an electron, respectively, in the presence of a soluble sacrificial reductant or oxidant. Here, we describe a novel application of these complexes in mediating light-induced changes in cellular electrical activity. We demonstrate that RubpyC17 ([Ru(bpy)(2)(bpy-C17)](2+), where bpy is 2,2'-bipyridine and bpy-C17 is 2,2'-4-heptadecyl-4'-methyl-bipyridine), readily incorporates into the plasma membrane of cells, as evidenced by membrane-confined luminescence. Excitable cells incubated in RubpyC17 and then illuminated at 488 nm in the presence of the reductant ascorbate undergo membrane depolarization leading to firing of action potentials. In contrast, the same experiment performed with the oxidant ferricyanide, instead of ascorbate, leads to hyperpolarization. These experiments suggest that illumination of membrane-associated RubpyC17 in the presence of ascorbate alters the cell membrane potential by increasing the negative charge on the outer face of the cell membrane capacitor, effectively depolarizing the cell membrane. We rule out two alternative explanations for light-induced membrane potential changes, using patch clamp experiments: (1) light-induced direct interaction of RubpyC17 with ion channels and (2) light-induced membrane perforation. We show that incorporation of RubpyC17 into the plasma membrane of neuroendocrine cells enables light-induced secretion as monitored by amperometry. While the present work is focused on ruthenium diimine complexes, the findings point more generally to broader application of other transition metal complexes to mediate light-induced biological changes.

| S-EPMC3629747 | biostudies-other

cis,cis,cis-(Acetato-κ(2) O,O')bis-[1,2-bis-(diphenyl-phosphan-yl)ethane-κ(2) P,P']ruthenium(II) 0.75-trifluoro-methane-sulfonate 0.25-chloride.

Project description:In the title Ru(II) carboxyl-ate compound, [Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25, the distorted tris-bidentate octa-hedral stereochemistry about the Ru(II) atom in the complex cation comprises four P-atom donors from two 1,2-bis-(diphenyl-phosphan-yl)ethane ligands [Ru-P = 2.2881 (13)-2.3791 (13) Å] and two O-atom donors from the acetate ligand [Ru-O = 2.191 (3) and 2.202 (3) Å]. The disordered counter-anions are located on the same site in the structure in a 3:1 ratio, the expanded formula comprising four complex cations, three trifluoro-methane-sulfonate anions and one chloride anion, with two such formula units in the unit cell.

| S-EPMC3629500 | biostudies-literature

Ruthenium-Catalyzed Site-Selective Trifluoromethylations and (Per)Fluoroalkylations of Anilines and Indoles.

Project description:Introducing (per)fluoroalkyl groups into arenes continues to be an interesting, but challenging area in organofluorine chemistry. We herein report an ortho-selective C-H perfluoroalkylation including trifluoromethylations of anilines and indoles without the need of protecting groups using Rf I and Rf Br as commercially available reagents. The availability and price of the starting materials and the inherent selectivity make this novel methodology attractive for the synthesis of diverse (per)fluoroalkylated building blocks, for example, for bioactive compounds and materials.

| S-EPMC7317475 | biostudies-literature