A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

One-Pot Reaction Sequence: N-Acylation/Pictet-Spengler Reaction/Intramolecular [4 + 2] Cycloaddition/Aromatization in the Synthesis of ß-Carboline Alkaloid Analogues.

One-pot synthesis of tetrahydro-ß-carbolines, fused with an isoindole core, was proposed starting from maleic anhydride and azomethines easily available from tryptamines and 3-(hetaryl)acroleins. This sequence includes four key steps: an acylation of the aldimine with maleic anhydride, a Pictet-Spengler cyclization, an intramolecular Diels-Alder reaction, and a concluding [1,3]-H shift. As a result, six- or seven-nuclear alkaloid-like heterocyclic systems, containing a benzo[1,2]indolizino[8,7-b]indole fragment annulated with furan, thiophene, or pyrrole, are formed in a diastereoselective manner.

Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity.

Unprecedented iron-based silsesquioxane/acetylacetonate complexes were synthesized. The intriguing cage-like structure of compounds is alkaline metal-dependent: the Fe2Li2 complex includes condensed Si6-silsesquioxane and four acetylacetonate ligands; the Fe4Na4 complex exhibits two cyclic Si4-silsesquioxane and eight acetylacetonate ligands, while the Fe3K3 complex features two cyclic Si3-silsesquioxane and six acetylacetonate ligands. The latter case is the very first observation of small trimeric silsesquioxane ligands in the composition of cage-like metallasilsesquioxanes. The Fe4Na4-based complex exhibits a record high activity in the oxidation of inert alkanes with peroxides (55% yield of oxygenates in cyclohexane oxidation). It also acts as a catalyst in the cycloaddition of CO2 with epoxides, leading to cyclic carbonates in good yields (58-96%).

Amine adducts of triallylborane as highly reactive allylborating agents for Cu(I)-catalyzed allylation of chiral sulfinylimines.

The implementation of selective catalytic processes with highly active reagents is an attractive strategy that meets the modern principles of sustainable development of chemistry. In the current study, we for the first time describe the method and general principles of Cu(I)-catalyzed allylation of imines with amine adducts of allylic triorganoboranes. Triallylborane is an extremely reactive compound and cannot be used for the catalytic allylation of imines, whereas its amine adducts are ideal substrates for catalysis. The structure of the amine fragment successfully balances the safety, selectivity and stability of the allylboron reagent, allowing it to demonstrate high activity in catalytic allylation reactions, exceeding many times any known allylboranes. The obtained results are supported by quantitative kinetics data and DFT calculations. The catalytic efficacy of the system was demonstrated on model sulfinylimines (23 examples). High diastereoselectivity up to >99% was achieved, including for the gram-scale synthesis of 2-hydroxyphenyl-derivatives. Taking into account the high reactivity and unsurpassed atom-economy of amine adducts of triallylborane (AAT), they can be considered as prospective allylation reagents with Cu(I) and other appropriate metallocatalysts.

Application of the intramolecular Diels-Alder vinylarene (IMDAV) reaction for the synthesis of benzo-, carbocyclo-, thienothiopheneisoindolecarboxylic acids and its limitations.

Thienylallylamines, readily accessible from the corresponding thienyl aldehydes, react with maleic and trifluoromethylmaleic anhydrides leading to the formation of acids with a thieno[2,3-f]isoindole core. The reaction sequence involves two successive steps: acylation of the nitrogen atom of the initial allylamine and the intramolecular Diels-Alder vinylarene (IMDAV) reaction. The scope and limitations of the proposed method were thoroughly investigated. It has been revealed with the aid of X-ray analysis and DFT calculations that the key step, the IMDAV reaction, proceeds through an exo-transition state, giving rise to the exclusive formation of a single diastereomer of the target heterocycle. The obtained functionally substituted thieno[2,3-f]isoindole carboxylic acids are potentially useful substrates for further transformations and bioscreening. The antimicrobial evaluation of the obtained compounds revealed that 1-oxo-2-(3-(trifluoromethyl)phenyl)hexahydrobenzo[4,5]thieno[2,3-f]isoindole-10-carboxylic acid is the most active sample in the synthesized library. It exhibits antibacterial activity against sensitive strains of Gram-positive bacteria, including S. aureus, Enterococcus faecium, Bacillus cereus, and Micrococcus luteus, as well as the Gram-negative bacteria E. coli and Pseudomonas fluorescens, with MIC values ranging from 4 to 64 µg mL-1. 9-Oxo-8-phenyloctahydronaphtho[2,1-d]thieno[2,3-f]isoindole-10-carboxylic acid showed antifungal activity against yeast culture C. albicans with a MIC value of 32 µM.

Halogen Bond-Assisted Supramolecular Dimerization of Pyridinium-Fused 1,2,4-Selenadiazoles via Four-Center Se2N2 Chalcogen Bonding.

The synthesis and structural characterization of α-haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles with various counterions is reported herein, demonstrating a strategy for directed supramolecular dimerization in the solid state. The compounds were obtained through a recently discovered 1,3-dipolar cycloaddition reaction between nitriles and bifunctional 2-pyridylselenyl reagents, and their structures were confirmed by the X-ray crystallography. α-Haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles exclusively formed supramolecular dimers via four-center Se···N chalcogen bonding, supported by additional halogen bonding involving α-haloalkyl substituents. The introduction of halogens at the α-position of the substituent R in the selenadiazole core proved effective in promoting supramolecular dimerization, which was unaffected by variation of counterions. Additionally, the impact of cocrystallization with a classical halogen bond donor C6F3I3 on the supramolecular assembly was investigated. Non-covalent interactions were studied using density functional theory calculations and topological analysis of the electron density distribution, which indicated that all ChB, XB and HB interactions are purely non-covalent and attractive in nature. This study underscores the potential of halogen and chalcogen bonding in directing the self-assembly of functional supramolecular materials employing 1,2,4-selenadiazoles derived from recently discovered cycloaddition between nitriles and bifunctional 2-pyridylselenyl reagents.

A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity.

This study reports a novel family of cage manganesesilsesquioxanes prepared via complexation with bathophenanthroline (4,7-diphenyl-1,10-phenanthroline). The resulting Mn4-, Mn6Li2-, and Mn4Na-compounds exhibit several unprecedented cage metallasilsesquioxane structural features, including intriguing self-assembly of silsesquioxane ligands. Complexes were tested in vitro for fungicidal activity against seven classes of phytopathogenic fungi. The representative Mn4Na-complex acts as a catalyst in the cycloaddition of CO2 to epoxides under solvent-free conditions to form cyclic carbonates in good yields.

Cage-like Cu5Cs4-Phenylsilsesquioxanes: Synthesis, Supramolecular Structures, and Catalytic Activity.

A small family of nonanuclear Cu5Cs4-based phenylsilsesquioxanes 1-2 were prepared by a convenient self-assembly approach and characterized by X-ray diffraction studies. The compounds 1 and 2 show some unprecedented structural features such as the presence of a [Ph14Si14O28]14- silsesquioxane ligand and a CuII5CsI4 nuclearity in which the metal cations occupy unusual positions within the cluster. Copper ions are "wrapped" into a silsesquioxane matrix, while cesium ions are located in external positions. This resulted in cesium-involved aggregation of coordination polymer structures. Both compounds 1 and 2 realize specific metallocene (cesium-phenyl) linkage between neighboring cages. Compound 2 is evaluated as a catalyst in the Baeyer-Villiger (B-V) oxidation of cyclohexanone and tandem cyclohexane oxidation/B-V oxidation of cyclohexanone with m-chloroperoxybenzoic acid (mCPBA) as an oxidant, in an aqueous acetonitrile medium, and HNO3 as the promoter. A quantitative yield of ε-caprolactone was achieved under conventional heating at 50 °C for 4 h or MW irradiation for 30 min (for cyclohexanone as substrate); 17 and 19% yields of lactone upon MW irradiation at 80 °C for 30 min and heating at 50 °C for 4 h, respectively (for cyclohexane as a substrate), were achieved. Complex 2 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with peroxides at 60 °C in acetonitrile. The maximum yield of cyclohexane oxidation products was 30%. Complex 2 exhibits high activity in the oxidation of alcohols.

4-Oxo-7-fluoro-1,10-phenanthroline-2,9-diamides: Synthesis, Structural Features, Lanthanide Complexes, and Am(III)/Ln(III) Solvent Extraction.

A highly efficient synthetic approach was developed for the synthesis of unsymmetrical 1,10-phenanthroline-2,9-diamides with two different substituents in the fourth and seventh positions of the phenanthroline core. The structures of these ligands were confirmed using various spectral methods including 2D-NMR and X-ray analysis. Quantum chemical calculations supported the presence of tautomeric forms of these ligands. Furthermore, it was discovered that these compounds exhibit polydentate ligand behavior toward lanthanide nitrates. The structural characteristics of the complexes formed between these ligands and lanthanide nitrates were investigated both in the solid state and in solution. To further understand the binding properties of these novel unsymmetrical ligands, the binding constants for potential complexes were quantitatively measured by using UV-vis spectrophotometric titration. This allowed for a comprehensive analysis of the binding affinity and stability of these complexes. Extraction experiments of f-elements were performed for symmetrical and unsymmetrical diamides. Overall, this study presents significant advancement in the synthesis and characterization of unsymmetrical 1,10-phenanthroline-2,9-diamides and provides valuable insights into their potential applications as polydentate ligands for lanthanide nitrates.

New 2,4-dihydro-1H-1,2,4-triazole-3-selones and 3,3'-di(4H-1,2,4-triazolyl)diselenides. Synthesis, biological evaluation, and in silico studies as antibacterial and fungicidal agents.

The reaction of aromatic ring-substituted isoselenocyanates with 2-thiopheacetic and 4-pyridinecarboxylic acid hydrazides yielded selenosemicarbazides which were further converted into previously unknown 1,2,4-triazole-3-selones and 3,3'-di(4H-1, 2,4-triazolyl)diselenides. The structures of the obtained compounds were studied by NMR spectroscopy, IR spectroscopy, and high-resolution mass spectroscopy (HR-MS). The bactericidal and fungicidal activity of some obtained compounds was evaluated in molecular modeling studies such as docking and simulation studies. The compound 3ba was reported as the most promising compound to show robust binding energy with different antibacterial and antifungal compounds. The compounds were observed in strong hydrophilic and hydrophobic interactions and remained in stable binding conformation with the receptor enzymes. Furthermore, the interatomic interaction energies were dominated by Van der Waals and electrostatic energies indicating the formation of stable complexes.

Chitosan-Based Antibacterial Films for Biomedical and Food Applications.

Antibacterial chitosan films, versatile and eco-friendly materials, have garnered significant attention in both the food industry and medicine due to their unique properties, including biodegradability, biocompatibility, and antimicrobial activity. This review delves into the various types of chitosan films and their distinct applications. The categories of films discussed span from pure chitosan films to those enhanced with additives such as metal nanoparticles, metal oxide nanoparticles, graphene, fullerene and its derivatives, and plant extracts. Each type of film is examined in terms of its synthesis methods and unique properties, establishing a clear understanding of its potential utility. In the food industry, these films have shown promise in extending shelf life and maintaining food quality. In the medical field, they have been utilized for wound dressings, drug delivery systems, and as antibacterial coatings for medical devices. The review further suggests that the incorporation of different additives can significantly enhance the antibacterial properties of chitosan films. While the potential of antibacterial chitosan films is vast, the review underscores the need for future research focused on optimizing synthesis methods, understanding structure-property relationships, and rigorous evaluation of safety, biocompatibility, and long-term stability in real-world applications.

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence-Synthesis, Structure, and Catalytic Activity.

A family of unusual octacopper cage methylsilsesquioxanes 1-4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1-4 due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of Cu8K2-based compound 2) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of Cu8Cs2-based compound 4). Cu8Cs2-complex 4 was evaluated in the catalysis of alkanes and alcohols. Complex 4 exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex 4 as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.

Acetone Factor in the Design of Cu4-, Cu6-, and Cu9-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes.

The present study describes a new feature in the self-assembly of cagelike copperphenylsilsesquioxanes: the strong influence of acetone solvates on cage structure formation. By this simple approach, a series of novel tetra-, hexa-, or nonacoppersilsesquioxanes were isolated and characterized. In addition, several new complexes of Cu4 or Cu6 nuclearity bearing additional nitrogen-based ligands (ethylenediamine, 2,2'-bipyridine, phenanthroline, bathophenanthroline, or neocuproine) were produced. Single-crystal X-ray diffraction studies established molecular architectures of all of the synthesized products. Several coppersilsesquioxanes represent a novel feature of cagelike metallasilsesquioxane (CLMS) in terms of molecular topology. A Cu4-silsesquioxane complex with ethylenediamine (En) ligands was isolated via the unprecedented self-assembly of a partly condensed framework of silsesquioxane ligands, followed by the formation of a sandwich-like cage. Two prismatic Cu6 complexes represent the different conformers─regular and elliptical hexagonal prisms, "cylinders", determined by the different orientations of the coordinated acetone ligands ("shape-switch effect"). A heterometallic Cu4Na4-sandwich-like derivative represents the first example of a metallasilsesquioxane complex with diacetone alcohol ligands formed in situ due to acetone condensation reaction. As a selected example, the compound [(Ph6Si6O11)2Cu4En2]·(acetone)2 was explored in homogeneous oxidation catalysis. It catalyzes the oxidation of alkanes to alkyl hydroperoxides with hydrogen peroxide and the oxidation of alcohols to ketones with tert-butyl hydroperoxide. Radical species take part in the oxidation of alkanes. Besides, [(Ph6Si6O11)2Cu4En2]·(acetone)2 catalyzes the mild oxidative functionalization of gaseous alkanes (ethane, propane, n-butane, and i-butane). Two different model reactions were investigated: (1) the oxidation of gaseous alkanes with hydrogen peroxide to give a mixture of oxygenates (alcohols, ketones, or aldehydes) and (2) the carboxylation of Cn gaseous alkanes with carbon monoxide, water, and potassium peroxodisulfate to give Cn+1 carboxylic acids (main products), along with the corresponding Cn oxygenates. For these reactions, the effects of acid promoter, reaction time, and substrate scope were explored. As expected for free-radical-type reactions, the alkane reactivity follows the trend C2H6 < C3H8 < n-C4H10 < i-C4H10. The highest total product yields were observed in the carboxylation of i-butane (up to 61% based on i-C4H10). The product yields and catalyst turnover numbers (TONs) are remarkable, given an inertness of gaseous alkanes and very mild reaction conditions applied (low pressures, 50-60 °C temperatures).

Crystallization Pathways of FABr-PbBr2-DMF and FABr-PbBr2-DMSO Systems: The Comprehensive Picture of Formamidinium-Based Low-Dimensional Perovskite-Related Phases and Intermediate Solvates.

In this study, we systematically investigated the phase diversity and crystallization pathways of the FABr excessive regions of two ternary systems of FABr-PbBr2-DMF and FABr-PbBr2-DMSO (where FA+-formamidinium cations, DMF-dimethylformamide and DMSO-dimethyl sulfoxide solvents). In these systems, a new FA3PbBr5 phase with a structure containing chains of vertex-connected PbBr6 octahedra is discovered, and its crystal structure is refined. We experimentally assess fundamental information on differences in the mechanisms of crystallization process in FABr-PbBr2-DMF and FABr-PbBr2-DMSO systems and determine possible pathways of crystallization of hybrid perovskites. We show that intermediate solvate phases are not observed in the system with DMF solvent, while a number of crystalline solvates tend to form in the system with DMSO at various amounts of FABr excess.

Robust Supramolecular Dimers Derived from Benzylic-Substituted 1,2,4-Selenodiazolium Salts Featuring Selenium⋯π Chalcogen Bonding.

The series of benzylic-substituted 1,2,4-selenodiazolium salts were prepared via cyclization reaction between 2-pyridylselenyl chlorides and nitriles and fully characterized. Substitution of the Cl anion by weakly binding anions promoted the formation supramolecular dimers featuring four center Se2N2 chalcogen bonding and two antiparallel selenium⋯π interactions. Chalcogen bonding interactions were studied using density functional theory calculations, molecular electrostatic potential (MEP) surfaces, the quantum theory of atoms-in-molecules (QTAIM), and the noncovalent interaction (NCI) plot. The investigations revealed fundamental role of the selenium⋯π contacts that are stronger than the Se⋯N interactions in supramolecular dimers. Importantly, described herein, the benzylic substitution approach can be utilized for reliable supramolecular dimerization of selenodiazolium cations in the solid state, which can be employed in supramolecular engineering.

Towards Anion Recognition and Precipitation with Water-Soluble 1,2,4-Selenodiazolium Salts: Combined Structural and Theoretical Study.

The synthesis and structural characterization of a series of supramolecular complexes of bicyclic cationic pyridine-fused 1,2,4-selenodiazoles with various anions is reported. The binding of trifluoroacetate, tetrachloroaurate, tetraphenylborate, perrhenate, and pertechnetate anions in the solid state is regarded. All the anions interact with selenodiazolium cations exclusively via a pair of "chelating" Se⋯O and H⋯O non-covalent interactions, which make them an attractive, novel, non-classical supramolecular recognition unit or a synthon. Trifluoroacetate salts were conveniently generated via novel oxidation reaction of 2,2'-dipyridyl diselenide with bis(trifluoroacetoxy)iodo)benzene in the presence of corresponding nitriles. Isolation and structural characterization of transient 2-pyridylselenyl trifluoroacetate was achieved. X-ray analysis has demonstrated that the latter forms dimers in the solid state featuring very short and strong Se⋯O and Se⋯N ChB contacts. 1,2,4-Selenodiazolium trifluoroacetates or halides show good solubility in water. In contrast, (AuCl4)-, (ReO4)-, or (TcO4)- derivatives immediately precipitate from aqueous solutions. Structural features of these supramolecular complexes in the solid state are discussed. The nature and energies of the non-covalent interactions in novel assembles were studied by the theoretical methods. To the best of our knowledge, this is the first study that regards perrhenate and pertechnetate as acceptors in ChB interactions. The results presented here will be useful for further developments in anion recognition and precipitation involving cationic 1,2,4-selenodiazoles.

Exploring Supramolecular Assembly Space of Cationic 1,2,4-Selenodiazoles: Effect of the Substituent at the Carbon Atom and Anions.

Chalcogenodiazoles have been intensively studied in recent years in the context of their supramolecular chemistry. In contrast, the newly discovered cationic 1,2,4-selenodiazole supramolecular building blocks, which can be obtained via coupling between 2-pyridylselenyl halides and nitriles, are virtually unexplored. A significant advantage of the latter is their facile structural tunability via the variation of nitriles, which could allow a fine tuning of their self-assembly in the solid state. Here, we explore the influence of the substituent (which derives from the nitrile) and counterions on the supramolecular assembly of cationic 1,2,4-selenodiazoles via chalcogen bonding.

Structural Organization of Dibromodiazadienes in the Crystal and Identification of Br···O Halogen Bonding Involving the Nitro Group.

Nitro functionalized dibromodiazadiene dyes were prepared and fully characterized including X-ray single crystal analysis. Electron deficient dibromodiazadienes were found to be able to act as donors of halogen bonding (XB), while the nitro group acted as an acceptor of the XB. Depending on the substituents, the Br···O XB competed with other weak interactions, and for some of the dyes, they even outcompeted the XB involving the nitro group. However, the nitro functionalized dibromoalkenes 6a and 10a, which had only the nitro moiety as the most plausible acceptor of the XB, reliably formed 1D chains via Br⋯O XB. Experimental work was supported by the DFT calculations and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method).

A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity.

The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1-9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1-9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7-9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.

Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity.

A series of phenylsilsesquioxane-benzoate heptacopper complexes 1-3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2-3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.