Recent Progress in Oxo- and Fluorometalate Chemistry

About a quarter of a century ago a review article having almost the same title appeared in this journal^[1]. Since then many hundreds of new fluorides and oxides of metals have been synthesized, and repeatedly subjected to detailed investigation. Why, and to what end are such compounds still studied^[2]? Has our knowledge been not only widened but also deepened? What advances have been made in synthetic chemistry in this sector? Have new ideas led to unforeseen results and have unexpected findings forced the revision of tested concepts? This area of research belongs to solid state chemistry, and in the meantime has become almost unsurveyable even for a committed researcher. In this paper, therefore, an attempt is made to outline any relevant advances that have been made and to present open questions and new aspects using selected examples, mainly from the chemistry of the first row of the transition metal series. Those not directly involved in this area may be surprised to find that even substances with a simple composition are also cited. They might ask whether such compounds mentioned in text books are not already understood. Although it is a widely-held view that such compounds are well known, this is incorrect: Probably no-one has ever prepared a sample of CrF₂ or Na₂O whose composition “adequately” exactly corresponded to the quoted formula^[3]. Typical examples which demonstrate the considerable effort necessary for finally proving what others long ago already assumed to know, can be taken from the area of inorganic chemistry (e.g.: As₂O) as well as from organic chemistry (e.g. C₄[C(CH₃)₃]).     

Antimalarial 20-membered macrolides from Streptomyces sp. BCC33756

Two new natural products, samroiyotmycins A (1) and B (2), along with two naturally new novclobiocin 101 (3) and 4-hydroxy-3-(3-methylbut-2-enyl)benzamide (5), and five known substances including neoantimycin, clorobiocin (4), 29-O-methylabierixin, daidzein, and 1-(3-indolyl)-2,3-dihydroxypropan-1-one have been isolated from Streptomyces sp. BCC33756. Their chemical structures were determined based on NMR spectral information and the relative stereochemistry of compound 1 was determined by X-ray crystallographic data. Both samroiyotmycins A and B exhibited antimalarial activity against Plasmodium falciparum K1—multi-drug resistant strain, with IC₅₀ values of 3.65 and 3.16 μg/mL, respectively. Compound 1 was inactive against both cancerous (MCF-7, KB) and non-cancerous (Vero) cells, while compound 2 displayed cytotoxicity against Vero cell with IC₅₀ value of 29.57 μg/mL.     

Influence of solvent strength in possible optimization of adsorption thin-layer chromatography

Considerations of TLC process optimization have been based on the thermodynamic theory of adsorption from multicomponent solvents using experimental and theoretical R_{M1, 2} = f (Φ₁) relationships. It was found that a relationship exists between the A_z parameter (log k where k is the partition coefficient of the substance chromatographed) of the above theory and pK_a values of substances as well as the solubility parameter δ of the mobile phase components. Analysis of the A_z values of substances shows that a slight variation therein is associated with lower selectivity of chromatographic separation.     

Synthesis,spectroscopic and crystal field studies on some azido-chromium(III)-pyridine complexes

The new complexes mer-Cr(py)₃(N₃)₃, NaCr(py)₄(N₃)₄, KCr(py)₄(N₃)₄, and RbCr(py)₃(N₃)₄ (py = pyridine) have been prepared. Infrared (4000-50 cm⁻¹) and diffuse reflectance spectra (region 300-77 K) of powdered samples have been measured and discussed on bases of the known structures of these complexes. Single crystal absorption spectra for the mer-complex were obtained in the temperature range from 300 to 10 K revealing extensive vibronic structure associated with the ²E_g(O_h) and ²T_1g(O_h) electronic origins. Crystal field calculations were used to assign the bands in the vibronic region and to obtain estimates for the crystal field and Racah parameters for this class of substances. The parameters found for the mer-complex at 10 K are 10 Dq = 17906 cm⁻¹, B = 387 cm⁻¹ and C = 3381 cm⁻¹.     

Low-temperature phase formation in CaF<Subscript>2</Subscript>–HoF<Subscript>3</Subscript> system

Phase formation in CaF₂–HoF₃ system has been studied by coprecipitation followed by X-ray powder diffraction. Aqueous nitrate solutions have been used as initial substances, while hydrofluoric acid has been employed as fluorinating agent. Formation of hydrated nanophases: solid solution Ca_1–x Ho _x F_{2 + x} (х ≤ 0.1) and HoF3 has been revealed. Dehydration proceeds on heating to 600°C.     

A Synthetic Intermediate for Trichothecane Phytotoxic Sesquiterpenoids

A number of sesquiterpenoid mold metabolites have been isolated and characterized recently. One important class of these naturally occurring substances, the trichothecane group, possesses an eminent degree of phytotoxic activity against certain pathogenic fungi.¹ The least structurally complicated member of this important class of mold metabolites is (-)-trichodermin (1). The structure and absolute stereochemistry of this unique phytotoxic metabolite was determined from chemical, spectroscopic, and X-ray diffraction data.^2,3,4 Recently Colvin, Raphael, and Roberts reported an elegant total synthesis of racemic trichodermin via (±)-lactone 2b (R[dbnd]CH₃).⁵ We wish to report, herein, a synthesis of optically active (+)-lactone 2b (R[dbnd]CH₃).⁶     

New complexes of the fac-{(CO)3Re} fragment bearing a diaminediphosphine ligand

The mono- and binuclear hydride compounds fac-[ReH(CO)₃L] (1a) and [{ReH(CO)₄}₂(μ-L)] (1b) have been prepared by reaction of [ReH(CO)₅] with Ph₂PN(CH₃)(CH₂)₂N(CH₃)PPh₂ (L) under UV light. Protonation reactions of the hydride compound 1a with equimolar amounts of HSO₃CF₃ or HCl yielded the triflato or the chlorido compounds fac-[Re(OSO₂CF₃)(CO)₃L] (2) and fac-[ReCl(CO)₃L] (3), respectively. The compounds have been characterised by elemental analysis, IR and NMR spectroscopic data, and mass spectrometry. Their structures have been confirmed by X-ray crystallography.     

d- and l-Serine, useful synthons for the synthesis of 24-hydroxyvitamin D3 metabolites. A formal synthesis of 1α,24R,25-(OH)3-D3, 24R,25-(OH)2-D3 and 24S,25-(OH)2-D3

d- and l-Serine have been used for the enantioselective synthesis of tosylates 7a and 7b, useful building blocks for the synthesis of triols 5a and 5b which have already been obtained via a diastereoselective synthesis and used for the synthesis of 2a, 2b and 2c. We have thus performed a formal synthesis of 24S,25-(OH)₂-D₃, 24R,25-(OH)₂-D₃ and 1α,24R,25-(OH)₃-D₃.     

Syntheses,crystal structures,and properties of two supramolecules based on methoxyphenyl imidazole dicarboxylates

Two cobalt(II) and cadmium(II) complexes, [Co(H₂DMOPhIDC)₂(H₂O)₂] ? 2H₂O (H₃DMOPhIDC = 2-(3,4-dimethoxyphenyl)-1H-imidazole-4,5-dicarboxylic acid) (I), [Cd(H₂MOPhIDC)₂-(Phen)] ? C₂H₅OH (H₃MOPhIDC = 2-(3-dimethoxyphenyl)-1H-imidazole-4,5-dicarboxylic acid, Phen = 1,10-phenanthroline) (II), have been hydro(solvo)thermally synthesized by employing two kinds of organic ligands, H₃DMOPhIDC or H₃MOPhIDC, respectively. The molecular structures of I and II have been characterized by IR spectra, elemental analyses and single-crystal X-ray diffraction (CIF files CCDC nos. 935845 (I), 935846 (II)). Both complexes show three-dimensional supramolecular structures supported by intermolecular H-bonds. Furthermore, the thermogravimetric and photoluminescent properties of two complexes have been investigated as well.     

Salen-type nickel(II), palladium(II) and copper(II) complexes having chiral and racemic camphoric diamine components

Chiral and racemic Salen-type Schiff-base ligands (H₂L¹, H₂L² and H₂L³), condensed between D-(+)- and D,L-camphoric diamine (also known as (1R,3S)-1,2,2-trimethylcyclopentane-1,3-diamine) and 2-hydroxybenzaldehyde or 3,5-dibromo-2-hydroxybenzaldehyde with a 1:2 molar ratio, have been synthesized and characterized. A series of new nickel(II), palladium(II) and copper(II) complexes of these chiral and racemic ligands exhibiting different coordination number (4, 5 and 6) have been characterized with the formulae [NiL¹]·CH₃OH (3), [NiL¹]·H₂O (4), [NiL²] (5), [PdL²] (6), [Cu₂(L²)₂(H₂O)] (7) and [NiL³(DMF)(H₂O)] (8). Different solvent molecules in 3 and 4 (methanol and water molecules) as well as different apical ligands in 7 and 8 (water and DMF molecules) are involved in different O–H···O hydrogen bonding interactions to further stabilize the structures. UV–Vis (UV–Vis), circular dichroism (CD) spectra and thermogravimetric (TG) analyses for the metal complexes have also been carried out.     

Ring opening of chiral 2-(1-aminoalkyl)epoxides by aliphatic thiols with total selectivity: synthesis of enantiopure 3-amino-1-(alkylthio)alkan-2-ols

We have studied the thiolysis of (2R,1′S)- or (2S,1′S)-2-(1-aminoalkyl)epoxides 1 or 2 in the presence of BF₃·OEt₂. The ring opening took place at C-3 with complete regioselectivity, affording the corresponding enantiopure (2R,3S)- or (2S,3S)-3-amino-1-(alkylthio)alkan-2-ols 3 or 4 in good or high yield. The structures of compounds 3 and 4 have been proposed based on HMBC NMR experiments.     

Reaction of carbonyl fluoride with fluorine in the presence of various fluorides as catalysts

The fluorides KF, RbF and CsF have been known to serve as catalysts for the reaction CF₂O + F₂→ CF₃OF. The list of catalysts for this process has now been enlarged to include NaF, MgF₂, CaF₂, SrF₂, BaF₂ and LaF₃. Lithium fluoride and thorium fluoride also give CF₃OF but are less active. Perhaps the substances CsF·HF, KAgF₄ and NiF₂ should be included in this list. Silver fluoride, usually as a mixture of AgF₂ with AgF, has been known to catalyze the reaction of CF₂O with F₂ to give both CF₃OF and CF₃OOCF₃. The proportion of the latter in the mixture of products increases with decreasing temperature. At 25°, the reaction is slow and the yield of CF₃OOCF₃ is very high. It has now been shown that TIF₃ behaves like silver fluoride. It has also been shown that many other fluorides of metals give higher yields of CF₃OOCF₃ than of CF₃OF but require higher temperatures than AgF₂ (100-ca. 150°) to be effective. Various possible mechanisms for these catalytic processes are discussed.     

Identification of phosphate anions in niobium and tantalum phosphates by means of infra-red spectra

Some niobium and tantalum phosphates have been prepared and their infra-red spectra have been recorded and compared with those of reference substances. It has been possible to identify P0₄^-3, P₂O₇^-4 and possibly P₃O10^-5 groups in different samples of niobium and tantalum phosphates.     

Beiträge zur Chemie des Phosphors. 117. Synthese und Eigenschaften der Hexaorganyl-octaphosphane(6) P8R6, R = Me,Et, Pri

Contributions to the Chemistry of Phosphorus. 117. Synthesis and Properties of the Hexaorganyl-octaphosphanes(6) P₈R₆, R = Me, Et, Prⁱ The Hexaorganyl-octaphosphanes(6) P₈Me₆ ( 1 ), P₈Et₆ ( 2 ), and P₈Pr ( 3 ) have been obtained by reacting mixtures of the corresponding organyldichlorophosphanes and phosphorus(III) chloride with magnesium. In the case of 1 and 2 the organyl-cyclophosphanes (PR)_n can also be used in the reaction with phosphorus(III) chloride and magnesium. Besides, mainly P₇R₅ as well as other polycyclic organylphosphanes are formed. 2 and 3 have been isolated as pure substances, whereas 1 was concentrated to ?50 mol-% in the product mixture. According to their ³¹P-NMR spectra the three compounds possess a pentalane-analogous P₈-skeleton with the substituents within each five-membered ring in trans position and the substituents of different five-membered rings next to the zero bridge in cis position; the organyl groups in the 3, 7 position are trans oriented with respect to the free electron pairs of the bridgehead atoms. Therefore, the structures of 1 – 3 differ from the known tert-butyl compound P₈Bu, whereas the corresponding phosphorus hydride P₈H₆ has the same pentalane-analogous P₈-skeleton, thus being a bicyclo[3.3.0]octaphosphane.     

Ultrafine α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals anchored on N-doped graphene: a nanomaterial with long hole diffusion length and efficient visible light-excited charge separation for use in photoelectrochemical sensing

The authors have coupled ultrafine α-Fe₂O₃ nanocrystals to N-doped graphene (NG) to obtain a novel material for use in a photoelectrode. The presence of NG is shown to strongly affect the morphology and size of the α-Fe₂O₃ nanocrystals formed on the NG sheets, and to improve their photoelectrochemical (PEC) activity. Interestingly, the PEC performance of the nanocomposite is closely correlated to the size of the α-Fe₂O₃ nanocrystals in that small nanocrystals display better PEC properties. The photocurrent of α-Fe₂O₃-NG is nearly 3.3-fold stronger than that of α-Fe₂O₃ nanocrystals. Based on the remarkable PEC performance of this nanocomposite, a PEC sensor was constructed for the sensitive determination of 1,4-dihydroxybenzene (HQ). Its photocurrent increases with the HQ concentration in the range from 3.0 nM to 3.3 μM, and the detection limit is 1.0 nM (at an S/N ratio of 3). In our perception, the study presented here can serve as a basis for a better understanding of the relationship between morphologies and PEC performance of such nanomaterials. Conceivably, it may be extended to other PEC sensing system and to other fields associated with nanotechnology.

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Graphical abstract Ultrafine α-Fe₂O₃ nanocrystals were prepared via coupling with N-doped graphene (NG) substances (α-Fe₂O₃-NG). They exhibit superior photoelectrochemical (PEC) performance and have been successfully utilized for PEC-based sensing.

     

Seven-coordinate rhenium(III) complexes of 1-(2-pyridylazo)-2-naphtholate: X-ray studies,spectroscopic characterization and DFT calculations

The reactions of [ReX₃(MeCN)(PPh₃)₂] (X = Cl or Br) with 1-(2-pyridylazo)-2-naphthol (HPAN) have been examined and the [ReBr(PAN)₂] · 2CHCl₃ (1) and [ReCl(PAN)₂] (2) complexes have been obtained. The both complexes have been structurally and spectroscopically characterized, and compound 1 has been additionally studied by magnetic measurements. The magnetic behavior is characteristic of mononuclear seven-coordinated Re(III) complex with d⁴ low-spin configuration, which gives diamagnetic ground state.     

Regioselective double intramolecular bridging of p-tert-butylcalix[7]arene

The first examples of doubly bridged calix[7]arenes 2a-h have been obtained by base-promoted O-alkylation of p-tert-butylcalix[7]arene 1 or 1,4-tetramethylene-bridged calix[7]arene 3a with a variety of bis-electrophiles including BrCH₂Cl, oligoethylene glycol ditosylates, and 1,2-bis(bromomethyl)benzene. In the presence of Cs₂CO₃ as the base, in acetone, the syn-1,4:2,3-bis-bridged regioisomer was obtained in yields up to 76%. Assignment of bridging pattern was based on chemical shift of OH groups in conjunction with chemical correlations with known compounds. Stereochemical and conformational features were investigated with the aid of 2D and Dynamic NMR studies and MM3 calculations.     

1-Methylimidazolin-2-yl functionalized cyclopentadienyl complexes of titanium and zirconium. Crystal structure of {[η:η-κN-C5H4CPh2CH2-(1-Me-C3H4N2)]ZrCl2}2(μ-Cl)2

The novel bidentate ligand, C₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂) (3), has been prepared and characterized as its lithium salt LiC₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂) (3-Li). Cyclopentadiene HC₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂) (3-H) has been obtained from 6,6-diphenylfulvene and 1,2-dimethylimidazoline (1). In THF-d₈ solution in the presence of 1, (1-methylimidazoline-2-yl)methyllithium (2) has been proved to undergo gradual conversion into a dilithium derivative of N¹-methyl-N²-[(1E,2E)-1-methyl-2-(1-methylimidazolidine-2-idene)ethylidene]ethane-1,2-diamine (2a). In a solution, cyclopentadiene 3-H has been shown to undergo isomerization into 3-{N-[2-(N-methylamino)ethyl]amino}-1,1-diphenyl-1,2-dihydropentalene (4) and, further, into a mixture of 4 and two rotameric 3-[N-(2-aminoethyl)-N-methylamino]-1,1-diphenyl-1,2-dihydropentalenes (5a) and (5b). Treatment of the lithium salt 3-Li with Me₃SiCl has lead to 3-{N-[2-(N-trimethylsilylamino)ethyl]amino}-1,1-diphenyl-1,2-dihydropentalene (6) as the dominant component in the reaction mixture. In the latter case the expected Me₃Si-C₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂) (3-Si) was not observed. Stannylation of 3-Li with 1 equiv. of Me₃SnCl has resulted in formation of a mixture of Me₃Sn-C₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂) (3-Sn), (Me₃Sn)₂-C₅H₃CPh₂CH₂-(1-Me-C₃H₄N₂) (3-Sn₂), and cyclopentadiene 3-H in a ca. 2:1:1 molar ratio. Monocyclopentadienyl complexes {[η⁵:η¹-κN-C₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂)]MCl₃ (M = Ti (7), Zr (8)) have been prepared starting from the organotin and organolithium compounds 3-Sn and 3-Li, respectively. The dynamic behavior of complexes 7 and 8 has been investigated by means of variable-temperature NMR spectroscopy in solutions. The molecular structures of the dihydropentalene 4, binuclear complex {[η⁵:η¹-κN-C₅H₄CPh₂CH₂-(1-Me-C₃H₄N₂)]ZrCl₂}₂(μ-Cl)₂8, and a coordination dimer of the dilithium salt 2a have been established by X-ray diffraction analysis. In the crystal structure of the 2a-dimer, the shortest known Li-Li contact has been found.     

Effect of the rigidity and flexibility features of 2-pyridinyl or 8-quinolinyl based N-N chiral ligands on the stereochemical properties of [Pd(N-N)Cl2] complexes

The [Pd(N-N^∗)Cl₂] complexes have been obtained, as yellow solids, in almost quantitative yields; N-N^∗ indicate bidentate chiral ligands (S_a)-1, (S_a)-2, (S,S)-3, (R,R)-4, containing the rigid 2-pyridinyl or 8-quinolinyl building block skeleton and the C₂-symmetric chiral framework trans-2,5-dimethylpyrrolidinyl or (S)-(+)-2,2′-(2-azapropane-1,3-diyl)-1,1′-binaphthalene. The ligands pairs have the same C₂-symmetric chiral framework but different building block skeleton, beyond that for the basicity in the N-donor atoms, for rigidity and flexibility features. The N-N^∗ ligands act as chelating ligands leading a square planar geometry. The compounds [Pd(S,S-3)Cl₂] and [Pd(R,R-4)Cl₂] have been also characterised by X-ray diffraction. The rigidity and flexibility features of (S,S)-3 and (R,R)-4 ligands induce a different orientation of the trans-2,5-dimethylpyrrolidinyl moiety with respect to the pyridinyl and quinolinyl plane. This work shows that intrinsic rigidity and flexibility are not enough to define the ligand properties and to preview the effects that they induce on the reactivity of the metal complex.     

Redox and catalase-like activities of four widely used carbon monoxide releasing molecules (CO-RMs)

The pathophysiological roles of the endogenous signaling molecule, carbon monoxide (CO), have been extensively studied and validated in cell culture and animal models. Further, evidence supporting the therapeutic effects of CO in various human diseases has been mounting over the last two decades. Along this line, there has been intensive interest in developing various delivery forms including CO gas, CO in solution, metal–carbonyl complexes widely known as CO-releasing molecules (CO-RMs), and organic CO prodrugs. Among them, two ruthenium-based carbonyl complexes, CORM-2 and -3, occupy a very special place because they have been used in over 500 published studies. One of the mechanisms for CO''s actions is known to be through attenuation of oxidative stress and regulation of production of reactive oxygen species (ROS). For this reason, it is important that CO delivery forms do not have intrinsic chemical redox properties. Herein, we describe our findings of catalase-like activities of CORM-2 and -3 in a CO-independent fashion, leading to the rapid degradation of hydrogen peroxide (H₂O₂) in PBS buffer (pH = 7.4) and in cell culture media. Further, we have found that CORM-2 and CORM-3 possess potent radical scavenging abilities. We have also studied two other widely used CO donors: CORM-401 and CORM-A1. Both showed chemical reactivity with ROS, but to a lesser degree than CORM-2 and -3. Because of the central role of ROS in some of the proposed mechanisms of actions for CO biology, the discovery of intrinsic chemical redox properties for these CO-RMs means that additional attention in designing proper controls is needed in future biological experiments using these CO-RMs for their CO-donating functions. Further, much more work is needed to understand the true implications of the chemical reactivity of these CO-RMs in cell-culture and animal-model studies of CO biology.

Four CO-releasing molecules are found to degrade H₂O₂ and free radicals either catalytically (CORM-2 and -3) or through direct reactions (CORM-401 and -A1) in solution under near-physiological conditions.