Methanol Ligands Research Articles

Substituted 2,2′‐Bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyl Complexes of Zinc

The condensation reaction of 2,2′‐diamino‐4,4′‐dimethyl‐6,6'‐dibromo‐1,1′‐biphenyl with 2‐hydroxybenzaldehyde as well as 5‐methoxy‐, 4‐methoxy‐, and 3‐methoxy‐2‐hydroxybenzaldehyde yields 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyl (1a) as well as the 5‐, 4‐, and 3‐methoxy‐substituted derivatives 1b, 1c, and 1d, respectively. Deprotonation of substituted 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls with diethylzinc yields the corresponding substituted zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls (2) or zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyls (3). Recrystallization from a mixture of CH2Cl2 and methanol can lead to the formation of methanol adducts. The methanol ligands can either bind as Lewis base to the central zinc atom or as Lewis acid via a weak O–H···O hydrogen bridge to a phenoxide moiety. Methanol‐free complexes precipitate as dimers with central Zn2O2 rings.

Formation of [Cu(CO2)(CH3OH)]+ and [Cu(N2)(CH3OH)]+ by gas-phase dissociation and exchange reactions

Electrospray ionization and multiple-stage tandem mass spectrometry were used to study the collision-induced dissociation of methanol-coordinated copper-acetate cations, and the ion-molecule reactions of specific product ions. Our experiments led to the discovery of unusual gas-phase ions with compositions such as [Cu(CO2)(CH3OH)]+ and [Cu(N2)(CH3OH)]+. The latter is generated by spontaneous exchange of CO2 for N2 in an ion-molecule reaction. Isotopic labeling studies and high mass-resolution measurements provide data to support the product ion composition assignments. Density functional theory calculations corroborate the experimental observations, both with respect to the preferential decarboxylation over methanol ligand elimination, and the spontaneous nature of the ion-molecule reactions.

The methanol sesquisolvate of sodium naproxen.

The asymmetric unit of the methanol solvate of sodium naproxen, systematic name: sodium (2S)-2-(6-meth-oxy-naphthalen-2-yl)propano-ate methanol sesquisolvate, Na+·C14H13O3 -·1.5CH3OH, comprises two formula units of the mol-ecular salt and three methanol mol-ecules. One of the sodium cations exhibits a coordination number of six and is bonded to three carboxyl-ate O atoms and three methanol OH groups whereas the second sodium cation has a coordination number of seven, defined by five carboxyl-ate O atoms and two methanol OH groups. Both coordination polyhedra around the sodium cations are considerably distorted. The two types of cations are bridged into polymeric chains extending parallel to [010]. This arrangement is stabilized by intrachain O-H⋯O hydrogen bonds between methanol ligands as donor and carboxyl-ate O atoms as acceptor groups. The hydro-phobic 6-meth-oxy-naphthyl moieties flank the hydro-philic sodium oxygen chains into ribbons parallel to [010]. There are no noticeable inter-molecular inter-actions between these ribbons. One of the 6-meth-oxy-naphthyl moieties is disordered over two sets of sites in a 0.723 (3):0.277 (3) ratio.

(η6-Benzene)Ru(II) half-sandwich complexes of pyrazolated chalcogenoethers for catalytic activation of aldehydes to amides transformation

The reaction of [(η6-C6H6)RuCl(μ-Cl)]2 with chalcogenoether substituted 1H-pyrazole ligands (L1-L3) in methanol have yielded three novel Ru(II) half-sandwich complexes [(η6-C6H6)RuCl(L)]PF6 (1–3) in high yield under the ambient reaction conditions. The NMR, MS and FT-IR analytical techniques were used to identify their structures. The molecular structures of the complexes 2 and 3 were established with X-ray crystallographic analysis and revealed a pseudo-octahedral half sandwich piano-stool geometry around ruthenium in each complex. Complexes 1–3 are thermally robust and were found to be insensitive towards the air and moisture. All the complexes were found to be catalytically active and produced the excellent yields of amides (up to 95%) from corresponding aldehydes. In contrast to the previous reported catalytic systems for aldehyde to amide transformation, the present complexes 1–3 are very efficient and have several advantages in terms of low catalyst loading, reaction time, temperature and wide applicability for various substituted aldehydes. Owing to the stronger σ-donor coordination properties of selenium containing ligands, the complex 2 was found to be more efficient as compare to the sulphur and tellurium analogues.

Crystal structure of a seven-coordinate manganese(II) complex with tris-(pyridin-2-ylmeth-yl)amine (TMPA).

Structural analysis of (acetato-κ2O,O')(methanol-κO)[tris-(pyridin-2-ylmeth-yl)amine-κ4N,N',N'',N''']manganese(II) tetraphenyl-borate, [Mn(C2H3O2)(C18H18N4)(CH3OH)](C24H20B) or [Mn(TMPA)(Ac)(CH3OH)]BPh4 [TMPA = tris-(pyridin-2-ylmeth-yl)amine, Ac = acetate, BPh4 = tetra-phenyl-borate] by single-crystal X-ray diffraction reveals a complex cation with tetra-dentate coordination of the tripodal TMPA ligand, bidentate coordination of the Ac ligand and monodentate coordination of the methanol ligand to a single MnII center, balanced in charge by the presence of a tetra-phenyl-borate anion. The MnII complex has a distorted penta-gonal-bipyramidal geometry, in which the central amine nitro-gen and two pyridyl N atoms of the TMPA ligand, and two oxygen atoms of the acetate ligand occupy positions in the penta-gonal plane, while the third pyridyl nitro-gen of TMPA and the oxygen from the methanol ligand occupy the axial positions. Within the complex, the acetate O atoms participate in weak C-H⋯O hydrogen-bonding inter-actions with neighboring pyridyl moieties. In the crystal, complexes form dimers by pairs of O-H⋯O hydrogen bonds between the coordinated methanol of one complex and an acetate oxygen of the other, and weak π-stacking inter-actions between pyridine rings. Separate dimers then undergo additional π-stacking inter-actions between the pyridine rings of one moiety and either the pyridine or phenyl rings of another moiety that further stabilize the crystal.

Cyclometalated Dicarbonyl Ruthenium Catalysts for Transfer Hydrogenation and Hydrogenation of Carbonyl Compounds

The dicarbonyl complex RuCl2(L)2(CO)2 (1) was easily prepared by reaction of ruthenium chloride hydrate with formic acid and L (L = (2,6-Me2C6H3)PPh2) in ethanol at reflux, via the [RuCl2(CO)2]n intermediate. Alternatively, 1 was obtained from [RuCl2(CO)3]2 and L by CO elimination. Reaction of 1 with NEt3 in toluene at reflux afforded the cyclometalated derivative RuCl{(2-CH2-6-MeC6H3)PPh2}(L)(CO)2 (2). A simple one-pot synthesis of 2 was achieved by treatment of RuCl3 hydrate with formic acid, L, and NEt3. The cyclometalated dicarbonyl complexes [Ru{(2-CH2-6-MeC6H3)PPh2}(NN)(CO)2]Cl (NN = ethylenediamine, 3; 2-(aminomethyl)pyridine, 4; (R,R)-1,2-diphenylethane-1,2-diamine, 5) were isolated by reaction of 2 with the corresponding dinitrogen ligand in methanol at reflux. Complexes 1–4 catalyze the transfer hydrogenation (TH) of acetophenone in 2-propanol at reflux (S/C = 1000 and TOF up to 30 000 h–1) with alkali base (1–5 mol %), whereas 5 leads to (S)-1-phenylethanol with 68% ee. The derivatives 1–5 cata...

Synthesis and characterization of Mono-Aqua-Pentakis (Isoni-Cotinic Acid) Nickel (II) Sulfate Trihydrate

A complex of nickel (II) with isonicotinic acid (asint) was successfully obtained. The complex was synthesized in 1:2 mole ratio of metal to the ligand in methanol. The percentage of nickel was 6.91% determined by Atomic Absorption Spectroscopy (AAS). Therefore, the predicted formula was Ni(asint)5SO4(H2O)4. The molar conductivity of the complex was measured by conductivity meter corresponding to 1:1 electrolyte. The thermal analysis of the formed complex was determined by Differential Thermal Analysis (DTA) indicating that the complex contains four water molecules as ligand and hydrates. The magnetic susceptibility measurement showed that the complex was paramagnetic with μeff= 3.30 B.M. Electronic spectra of the formed complex appeared at two transition peaks on λ= 394 nm and 659 nm. The infrared spectra of the complex showed a shift of tertiary N-group absorption in 1234 and 1338 cm-1 compared to isonicotinic acid at 1149 and 1331 cm-1. In addition, the shift also appeared in the -OH group absorption which was to the lower wavenumber at 3371 cm-1 from 3425 cm-1 (isonicotinic acid). This fact indicated that the functional groups were coordinated to the central metal ion. The possibility formula of the complex was [Ni(asint)5(H2O)]SO4·3H2O with octahedral structure.

Synthesis and Characterization of Tetrakis(2-amino-3-methylpyridine)copper(II) Sulfate Tetrahydrate

The complex of Tetrakis(2-amino-3-methylpyridine)copper(II) sulfate tetrahydrate has been synthesized in a ratio of 1: 6 metal to ligand in methanol. The percentage of copper in the complex measured by Atomic Absorption Spectrometer (AAS) showed the complex formula was Cu(2-amino-3-metilpyridine)4SO4(H2O)n (n = 3, 4, or 5). The analysis of TG/DTA showed that 1 mole of complex contains 4 moles of H2O. The conductivity measurement indicated that the complex is in 1 to 1 electrolyte. The formula of the complex was estimated as [Cu(2-amino-3-metilpyridine)4]SO4·4H2O. The complex was paramagnetic with µeff of 1.85 BM. The UV-Vis spectra showed a band peak at 730 nm with an electronic transition Eg→T2g. IR spectral data indicated that the functional groups of N-pyridine 2-amino-3-metilpyridine coordinated to ion Cu(II). The geometry of the complex was probably square planar.

Synthesis and Characterization of Tetrakis-aqua-bis-isonicotin-amide(itmd)nickel(II) Sulfate

The complex of Tetrakis-aqua-bis-(isonicotinamide)nickel(II) sulfate has been synthesized in 1:2 mole ratio of metal to ligands in methanol. The formula of the complex predicted from analysis nickel content in the complex by Atomic Absorption Spectroscopy (AAS) was Ni(itmd)2SO4(H2O)4. The conductivity of the complex in methanol was measured by conductivity meter correspond to 1:1 electrolyte. Thermal analysis of the complex was determined by Differential Thermal Analyzer (DTA) indicating that the complex contains four H2O molecules as ligands. The magnetic susceptibility measurement showed that the complex was paramagnetic with μeff = 3.02 BM. The electronic spectra of the complex appear due to two transition peak on λ = 398 nm and 664 nm. The Infrared spectra showed a shift of NH2 stretching vibration of Ni(itmd)2SO4(H2O)4. These facts indicated that these functional groups were coordinated to the center ion of the complexes. The proposed structure of the complex was octahedral therefore the possibility formula of this complex was [Ni(itmd)2(H2O)4]SO4.

Synthesis and Characterization of A Coordination Complex of Tetrakis(diphenylamine)copper(II) Sulfate Hexahydrate

CuSO4·5H2O with diphenylamine formed a complex compound in 1:4 mole ratio of metal to the ligand in methanol. The forming of the complex was indicated by shifting of UV-Vis spectra of CuSO4·5H2O and the complex from 819 nm to 593 nm. The result of analysis Cu(II) in the complex showed the copper content in the complex was 6.43 % therefore the empirical formula of the complex was Cu(diphenylamine)4SO4(H2O)6. The electrical conductivity of complex showed the charge ratio of cation and anion = 1:1. Therefore, the proposed formula of the complex was [Cu(diphenylamine)4]SO4·6H2O. Based on infrared spectra, it was determined that the functional group of N-H of diphenylamine was coordinated to the center ion Cu2+. The electronic spectral study of the complex showed a transition peak on λ = 593 nm (υ = 16863 cm-1) corresponding to the 2B1g → 2A1g transition. The complex was paramagnetic with effective magnetic moment 1.72 B.M. It was indicated square planar geometry around Cu(II).

Synthesis, crystal structure, electrochemical properties and DFT calculations of three new Zn(II), Ni(II) and Co(III) complexes based on 5-bromo-2-((allylimino)methyl)phenol Schiff-based ligand

Abstract In this work, a new Schiff base ligand (HL: 5-bromo-2-((allylimino)methyl)phenol) was prepared from the reaction of 5-bromo salicylaldehyde and allylamine. Then, three new Schiff base complexes, ZnL2 (1), NiL2 (2) and CoL3 (3), were synthesized through the reaction of Zn(NO3)2·6H2O, Ni(OAC)2·4H2O, and CoCl2·6H2O with the new Schiff base ligand in methanol or chloroform. The ligand and its related complexes were characterized by elemental analysis, FT-IR, UV-Vis spectroscopy, and 1H- NMR technique. The molecular structures of complexes (1–3) were determined by the single crystal X-ray diffraction technique. The crystallographic data revealed that complexes 1 and 2 are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two Schiff base ligands. On the other hand, the metal center is six-coordinated by three phenolate oxygen and three imine nitrogen atoms of three Schiff base ligands in 3. Eventually, DFT calculations and the study of electrochemical properties were performed on the new three complexes.

Pd-bound functionalized mesoporous silica as active catalyst for Suzuki coupling reaction: Effect of OAcˉ, PPh3 and Clˉ ligands on catalytic activity

Three new palladium catalysts, PdCat-I, PdCat-II and PdCat-III, immobilized over heterogeneous silica support have been synthesized using different ligands attached to the palladium precursor. The ligands that have been used in this study are acetate, triphenylphosphine and chloride in PdCat-I, PdCat-II and PdCat-III, respectively. The ligands have different effect on stability of the compounds and impart different oxidation states to the metal center. The materials have been characterized by powder X-ray diffraction, nitrogen adsorption-desorption studies, transmission electron microscopy, thermal analysis, and different spectroscopic techniques. The Pd-content of the samples have been determined by ICP-AES analysis. The materials have been used as catalysts for Suzuki coupling reaction of aryl halides with phenylboronic acid under mild conditions. A comparative study has been carried out to ascertain the effect of the nature of different ligands on the outcome of the catalytic reactions. Products have been identified and estimated by 1H NMR and gas chromatography. The results show that the best yields are obtained with the catalyst containing triphenylphosphine as the ligand in methanol. Such type of work to study the effect of ligand on Suzuki coupling reaction over functionalized mesoporous silica heterogeneous catalysts have not been carried out so far.

Regioselective B-H/C-H activation and metal-metal bond formation induced by half-sandwich metals complexes at hydroxy-substituted o-carboranes.

A binuclear iridium complex, (Cp2*Ir2(CH2O)C2B10H8) (6), with a unique metal-metal bond has been synthesized and fully characterized. Importantly, this complex is constructed via selective C-H and B(3)-H bond activation on the carborane precursor. Additionally, when the proligand (2-pyridine)(o-carboranyl)methanol ligand was combined with a half-sandwich iridium complex, selective B(6)-H bond activation or metal-carbon bond formation can be induced by the use of different bases. And the rhodium complex constructed from (2-pyridine)(o-carboranyl)methanol ligand containing a metal-carbon bond has been obtained and fully characterized.

Synthesis, crystal structures, and application of two new pincer type palladium(II)-Schiff base complexes in C-C cross-coupling reactions

Two new pincer type Pd(II)-Schiff base complexes of the general formula [PdL1(PPh3)] 1 and [PdL2(PPh3)] 2, (where L1 = 2-(2,3-Dihydroxybenzylideneamino)phenolate and L2 = 2-(2,3-dihydroxybenzylidene)hydrazinecarbothioamidate) were synthesised by the reaction of the palladium acetate with the corresponding ligand in methanol as yellow crystalline solids in high yields. Both complexes were fully characterized by FT-IR, 1H NMR, 13C NMR, 31P NMR, elemental analysis and single crystal X-ray diffraction studies. The crystal structures confirmed the tridentate nature of the pincer type Schiff base ligands and the distorted square planar geometry around the metal centre in both cases. The triphenylphosphine acted as an auxiliary ligand and occupied the fourth coordination site at palladium. The complexes were found to be efficient homogenous catalysts for a series of Suzuki-Miyaura, Heck-Mizoroki and Sonogashira reactions at a low catalyst loading (0.08 mol%), and without the use of any additives. All organic products were fully characterized by 1H and 13C NMR studies.

Zinc(II) halide complexes with 2-methoxyaniline ligand: Synthesis, characterization, thermal analyses, crystal structure determination and luminescent properties

Three new mononuclear zinc(II) complexes, [Zn(2-MeO-C6H4NH2)2X2] (X is Cl in 1, Br in 2 and I in 3), were prepared from the reactions of ZnX2 with 2-methoxyaniline (2-MeO-C6H4NH2) ligand in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurements by slow evaporation of methanol solution at room temperature. The three complexes were thoroughly characterized by thermogravimetric analysis, elemental analysis (CHNO), spectral methods (IR, UV–Vis, 13C{1H}NMR, 1H NMR and luminescence), and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the zinc(II) cation is four-coordinated in a distorted tetrahedral configuration by two N atoms from two 2-methoxyanyline ligands and two halide anions. Also, in these complexes intermolecular interactions, for example NH⋯X hydrogen bonds (in 1–3), CH⋯X hydrogen bonds (in 3), CH⋯π interactions (in 1 and 2) and π⋯π interactions (in 3), are effective in the stabilization of the crystal structures. In addition, the luminescence spectra of all complexes in methanolic solution show that the intensity of their emission bands is stronger than that for free 2-methoxyaniline ligand.

Synthesis and Elucidation Structure of Tetrakis-diphenylaminecopper(II) Chloride Hexahydrate

CuCl2·2H2O with diphenylamine formed a complex compound in 1:4-mole ratio of metal to the ligand in methanol. Its structural properties were investigated by employing metal content analysis by Atomic Absorption Spectroscopy (AAS), magnetic susceptibility, UV-vis and FTIR spectroscopy. The forming of the complex was indicated by shifting of UV-Vis spectra. The result of analysis Cu(II) in the complex showed empirical formula of the complex were Cu(diphenylamine)4Cl2(H2O)6. The electrical conductivity of complex showed the charge ratio of cation and anion = 2:1. Finally, the proposed formula of the complex was [Cu(diphenylamine)4]Cl2·6H2O. Based on infrared spectra, it was revealed that diphenylamine existed as monodentate bind to copper(II) through the functional group of N-H. The electronic spectral study of the complex showed three transition peaks on 861, 592, and 419 nm corresponding to the 2B1g → 2A1g, 2B1g → 2B2g dan 2B1g → 2Eg transitions. The complex was paramagnetic and indicated that ligands form square planar geometry around the Cu(II).

Template synthesis of two new supramolecular zinc(II) complexes containing pentadentate N3O2 semicarbazone ligand: Nanostructure synthesis, Hirshfeld surface analysis, and DFT studies

Two new zinc(II) complexes, [Zn(H2dapsc) (CH3OH)2][ZnBr2Cl2] (1) and [Zn(H2dapsc) (CH3OH)Br]Br.(CH3OH) (2), where H2dapsc is 2,6-diacetylpyridine bis(semicarbazone), were synthesized using a template method in which the pentadentate N3O2 semicarbazone ligand derived from [1 + 2] condensation of 2,6-diacetylpyridine and semicarbazide in the presence of zinc(II) ion as template agent. These compounds were characterized by IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Their single crystal X-ray structures showed that in both complex cations, the metal center has a distorted pentagonal-bipyramidal geometry in which the semicarbazone (H2dapsc) ligand occupies the equatorial plane, while the axial positions occupy by two methanol ligands in (1) and two bromo and methanol ligands in (2). Furthermore, the impact of the close intermolecular contacts on the crystal packing of (1) and (2) have been further studied using Hirshfeld surface analysis. Density Functional Theory (DFT) method was applied for the calculation of HOMO-LUMO energy gap, atomic charges and vibrational frequencies of title complexes. Moreover, the nanostructure of zinc complex was synthesized by a sonochemical method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy, and elemental analysis.

Trinuclear and polymeric cobalt(II or II/III) complexes with an arylhydrazone of acetoacetanilide and their application in cyanosilylation of aldehydes

The new trinuclear [CoII(H2O)2(Me2NCHO)2{CoIII(1κNOO′:2κO″-μ-HL)}2(1κNOO′)]·2H2O (1) and polymeric [CoII(1κNOO′:2κO″-μ-HL)(MeOH)2]n (2) complexes were isolated by the reaction of (Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)benzoic acid (H3L) with CoCl2·6H2O and Co(ClO4)2·6H2O, respectively, in a mixture of DMF/MeOH (1/10, v/v), in the presence of Et3N at room temperature, and characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses. In both structures the cobalt centres display distorted octahedral geometries. The structural units in 1 and 2 are connected via intermolecular hydrogen bonds involving the coordinated HL2− and the bound and non-bound water molecules (in 1) or the methanol ligands (in 2) which provides supramolecular networks. 1 and 2 are catalyst precursors for the cyanosilylation reaction of a variety of both aromatic and aliphatic aldehydes with trimethylsilyl cyanide leading to the corresponding cyanohydrin trimethylsilyl ethers in high yields (up to 89%) in methanol and at room temperature.

Preparation, spectroscopic and structural study of copper(II) complexes derived from bulky pyridine ligands

Three different binuclear tetracarboxylato-bridged copper(II) complexes supported by bulky pyridines ligands [Cu(µ-MeCO2)2(dPy)]2 (dPy=3-phenylpyridine (1), 2-benzylpyridine (2) and 4-acetylpyridine (3)) have been synthesised. These compounds were obtained from reaction of [Cu(MeCO2)2(H2O)]2 with pyridine-derived ligands in methanol at room temperature. All compounds were fully characterized by analytical and spectroscopic methods. The molecular structures were determined by X-ray diffraction analysis. All compounds consist of binuclear units where both Cu(II) atoms are linked by four syn–syn carboxylates bridges, showing a paddle-wheel unit, and exhibit interesting intermolecular interactions in the outer coordination sphere.

Triol-Ligand Modification and Structural Transformation of Anderson-Evans Oxomolybdates via Modulating Oxidation State of Co-Heteroatom.

Various covalent decorations and structural transformations of a series of R-C(CH2OH)3 triol ligands on CoII/CoIII-centered Anderson-Evans polyoxomolybdates were studied in aqueous and/or organic solution. Single-crystal X-ray structural analysis demonstrated that four manners, including (1) double-sided χ/χ-isomer and (2) double-sided δ/χ-isomer with CoII central heteroatom, and (3) single-sided δ-isomer and (4) double-sided δ/δ-isomer with CoIII central heteroatom, appeared on the decoration of the mother polyanion [CoII/III(OH)6Mo6O18]4-/3-. Through careful manipulation of the reaction conditions, a gradual oxidation process from CoII to CoIII was disclosed to happen in air, and accompanying that process, the CoII-centered double-sided δ/χ-isomer that formed in the initial stage transformed into a CoIII-centered double-sided δ/δ-isomer. When the electron-withdrawing group -NO2 substituted triol ligand was used to replace CH3C(CH2OH)3, the oxidation process accelerated spontaneously. A further investigation showed that this oxidation process can be blocked by acid. While the triol ligands' decoration on Anderson-Evans polyoxometalates (POMs) took place along with the oxidation of the central heteroatom, that codecoration of other components was also accomplished. In the presence of excess acetic acid, an unprecedented single-sided δ-isomer with an acetate ligand covalently attaching on the other side by replacing one μ3-O atom was obtained in aqueous solution. The reaction of the mother cluster [(n-C4H9)4N]3[Co(OH)6Mo6O18] and triol ligands in methanol resulted in a codecoration of methanol with the double-sided δ/δ-isomer, which has never been reported in B-type Anderson-Evans POMs. The obtained results revealed that the oxidation state of the heteroatom has a significant impact on the triol ligand decoration styles, such as the χ/χ- or δ/χ-isomer for the divalent heteroatom and the δ- or δ/δ-isomer for the trivalent heteroatom.