N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)_2]·(2-sb)·2H_2O(1),[Pt(NIA)_2]·(3-sb)·3H_2O(2)和[Pt(NIA)_2]·(1,4-dsb)·2H_2O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb~2-=2-磺基苯甲酸二价阴离子、3-sb~2-=3-磺基苯甲酸二价阴离子、1,4-dsb~2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb~2-转变为1,4-dsb~2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)_2]~(2+),中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)₂]·(2-sb)·2H₂O(1),[Pt(NIA)₂]·(3-sb)·3H₂O(2)和[Pt(NIA)₂]·(1,4-dsb)·2H₂O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb^2-=2-磺基苯甲酸二价阴离子、3-sb^2-=3-磺基苯甲酸二价阴离子、1,4-dsb^2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb^2-转变为1,4-dsb^2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)₂]²⁺,中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

X-ray Crystal and Ab Initio Structures of 3′,5′-di-O-Acetyl-N(4)-Hydroxy-2′-Deoxycytidine and Its 5-Fluoro Analogue: Models of the N(4)-OH-dCMP and N(4)-OH-FdCMP Molecules Interacting with Thymidylate Synthase

The crystal and molecular structures of the 3′,5′-di-O-acetyl-N(4)-hydroxy-2′-deoxycytidine molecule and its 5-fluoro congener have been determined by X-ray single crystal diffraction. The 3′,5′-di-O-acetyl-N(4)-hydroxy-5-fluoro-2′-deoxycytidine molecule crystallizes in the space group C2 with the following unit cell parameters: a = 21.72 Å, b = 8.72 Å, c = 8.61 Å, and β = 90.42^∘. 3′,5′-di-O-acetyl-N(4)-hydroxy-2′-deoxycytidine also belongs to the monoclinic space group C2 and the unit cell parameters are: a = 39.54 Å, b = 8.72 Å, c = 22.89 Å, and β = 95.26^∘. The non-fluorine analogue demonstrates a rare example of crystal structure with five symmetry-independent molecules in the unit cell. All the molecules in both crystal structures have the sugar residue anti oriented with respect to the base, as well as have the N(4)-OH residue in cis conformation relatively to the N(3)-nitrogen atom. In addition to the molecular geometries from X-ray experiment, the optimized molecular geometries have been obtained with the use of theoretical ab initio calculations at the RHF/6-31G(d) level. The corresponding geometric parameters in the molecules of 3′,5′-di-O-acetyl-N(4)-hydroxy-2′-deoxycytidine and its 5-fluoro congener have been compared. The differences including the C(5)=C(6) bond shortening and C(4)—C(5)—C(6) angle widening in the fluorine analogue are discussed in this paper in relation to the molecular mechanism of enzyme, thymidylate synthase, inhibition by N(4)-hydroxy-2′-deoxycytidine monophosphate and its 5-fluoro congener.     

Study on structural properties and solution dynamics of zinc complexes with the (N,N-dimethylaminomethyl)ferrocenyl ligand

The reaction of {C,N-[Fe(η⁵-C₅H₅)(η⁵-C₅H₃(CH₂NMe₂)-2)]}Li, (FcN)Li, with zinc chloride affords the diorganozinc complex (FcN)₂Zn (1). In solution, 1 appears as a mixture of rac and meso diastereomers, whereas in the solid state it crystallizes solely as a rac diastereomer. The ratio of rac/meso diastereomers in solution is solvent-, temperature- and concentration-dependent, consistent with an intermolecular exchange between diastereomers. An intramolecular dynamic phenomenon involving dissociation and recoordination of Zn---N bonds was also observed. The reaction of 1 with zinc chloride yields the monoorganozinc compound (FcN)ZnCl (2) as a slightly soluble yellow microcrystalline powder.     

Structure and DFT calculations of 2-{[3-methyl-3-phenyl-cyclobutyl)-thiazol-2-yl]-hydrazonomethyl}-phenol

The title compound 2-{[3-Methyl-3-phenyl-cyclobutyl)-thiazol-2-yl]-hydrazonomethyl}-phenol (C₂₁H₂₁N₃S₁O₁) crystallizes in the P-1 triclinic space group with a = 5.8880(4) ?, b = 9.5618(5) ?, c = 17.0484(10) ?, α = 80.214(5)°, β = 80.532(5)°, γ = 80.116(5)°. In addition to molecular geometry and packing from X-ray experiment, we have also calculated the molecular geometry and vibrational frequencies of the title compound in the ground state using density functional theory DFT (B3LYP) with the 6–31G(d,p) basis set. Apart from this, the structure of the title compound is characterized by ¹H NMR, ¹³C NMR, IR and UV-vis. Spectra, and the experimental emission energies are compared with the HOMO-LUMO energy gaps calculated by the DFT method.     

Synthesis and reactivity of neodymium(III) amido-tethered N-heterocyclic carbene complexes

The reaction of the heteroleptic Nd(III) iodide, [Nd(L′)(N″)(μ-I)] with the potassium salts of primary aryl amides [KN(H)Ar′] or [KN(H)Ar^*] affords heteroleptic, structurally characterised, low-coordinate neodymium amides [Nd(L′)(N″)(N(H)Ar′)] and [Nd(L′)(N″)(N(H)Ar^*)] cleanly (L′ = t-BuNCH₂CH₂[C{NC(SiMe₃)CHNt-Bu}], N″ = N(SiMe₃)₂, Ar′ = 2,6-Dipp₂C₆H₃, Dipp = 2,6-Prⁱ₂C₆H₃, Ar^* = 2,6-(2,4,6-Prⁱ₃C₆H₂)₂C₆H₃). The potassium terphenyl primary amide [KN(H)Ar^*] is readily prepared and isolated, and structurally characterised. Treatment of these primary amide-containing compounds with alkali metal alkyl salts results in ligand exchange to give alkali metal primary amides and intractable heteroleptic Nd(III) alkyl compounds of the form [Nd(L′)(N″)(R)] (R = CH₂SiMe₃, Me). Attempted deprotonation of the Nd-bound primary amide in [Nd(L′)(N″)(N(H)Ar^*)] with the less nucleophilic phosphazene superbase Bu^tNP{NP(NMe₂)₃}₃ resulted in indiscriminate deprotonations of peripheral ligand CH groups.     

Enantioselective syntheses of no-carrier-added (n.c.a.) (s)-4-chloro-2-[f] fluorophenylalanine and (s)-(α-methyl) -4-chloro-2-[f]fluorophenylalanine

(S)-4-Chloro-2-fluorophenylalanine and (S)-(α-methy)-4-chloro-2-fluorophenylalanine were synthesized and labeled with no carrier added (n.c.a.) fluorine-18 through a radiochemical synthesis relying on the highly enantioselective reaction between 4-chloro-2-[¹⁸F]fluorobenzyl iodide and the lithium enolate of (2S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3-methyl-1,3-imidazolidine-4-one for (S)-4-chloro-2-[¹⁸F]fluorophenylalanine and (2S,5S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3,5-dimethyl-1,3-imidazolidine-4-one for (S)-(α-methyl) -4-chloro-2-[¹⁸F] fluorophenylalanine. Quantities of about 20–25 mCi were obtained at the end of sy nthesi s, ready for injection after hydrolysis and high performance liquid chromatography (HPLC) purification, with a radiochemical yield of 17%–20% corrected to the end of bombardment after a total synthesis time of 90–105 min from [¹⁸F] fluoride. The enantiomeric excesses were shown to be 97% or more for both molecules without chiral separation and the radiochemical and chemical purities were 98% or better.     

Synthesis of elastomeric polypropylene in bulk using C 1-symmetric ansa-metallocenes. New aspects of the synthesis of 1-(fluoren-9-yl)-2-(2-methyl-5,6-dihydrocyclopenta [f]-1H-inden-1-yl)ethane and complexes of zirconium and hafnium with this ligand

Isomeric 1-(fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-1 H-indenyl) ethanes 1a,b and C ₁-symmetric metallocenes, viz., rac-1-(η⁵-fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-η⁵-inden-1-yl) ethanezirconium dichloride (9) and rac-1-(η⁵-fluoren-9-yl)- 2-(2-methyl-5, 6-dihydrocyclopenta [f]η⁵-inden-1-yl)ethanehafnium dichloride (10), with these ligands were synthesized by modified procedures. The structures of compounds 1b (two crystalline modifications) and 10 were established by X-ray diffraction analysis. The synthesis of polypropylene (PP) in bulk was studied in the presence of polymethylalumoxane-activated metallocenes 9 and 10 in the temperature range of 30–70°C. It was demonstrated that triisobutylaluminum can be used as a cocatalyst. In this case, the molecular weight of PP increases by a factor of ∼2. An increase in the reaction temperature leads to an increase in stereoregularity and crystallinity of PP. The polymer synthesized at high temperatures crystallizes in the γ form. The resulting PP is characterized by a wide range of properties from rigid crystalline thermoplastic to amorphous elastomeric. Samples, which have a high molecular weight and moderate isotacticity, exhibit high elastomeric and durability properties.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 400–413, February, 2005.     

Volumetric and transport properties of binary liquid mixtures of N-methylacetamide with lactones at temperatures (303.15 to 318.15) K

The values of density (ρ), viscosity (η) and speed of sound (u) have been measured for binary liquid mixtures of γ-butyrolactone (GBL), δ-valerolactone (DVL), and ε-caprolactone (ECL) with N-methylacetamide (NMA) over the whole composition range at T = (303.15 to 318.15) K and atmospheric pressure. From these data, excess molar volume (V^E), deviation in viscosity (Δη), and deviation in isentropic compressibility (Δκ_s), are calculated. The results are fitted to a Redlich–Kister type polynomial equation to derive binary coefficients and standard deviations.     

Dispersity of stratum corneum in the mixed aqueous solutions of binary mixtures between N,N-dimethyldodecylamine oxide and sodium dodecyl sulfate or two terpenes

Solubilization of cholesterol, differential scanning calorimetric (DSC), nuclear magnetic resonance (NMR) and dynamic light scattering (DLS) measurements were performed in order to reveal the dispersion mechanisms of stratum corneum (SC) into each intact corneocytes in the following systems: (1) in the aqueous mixed solutions of sodium dodecyl sulfate (SDS) and N,N-dimethyldodecylamine oxide (C₁₂DMAO); (2) in the aqueous micellar solutions of C₁₂DMAO containing solubilized α-terpineol (α-T); and (3) in the aqueous micellar solutions of C₁₂DMAO containing solubilized limonene. The intercellular lamellar structure of SC was revealed to be disrupted and/or removed in all these solutions. However, considering the micellar sizes and the interaction among molecules in micelle, the dispersion mechanisms in these three systems were different each other. The three dispersion mechanisms of SC were estimated and discussed on the basis of the results of solubilization, DSC, NMR and DLS, respectively.     

The crystal structure, vibrational spectra, and thermal behavior of dilithium piperazinium(2+) selenate tetrahydrate and dilithium N,N′-dimethylpiperazinium(2+) selenate tetrahydrate

The crystal structure of dilithium piperazinium(2+) selenate tetrahydrate has been solved; this substance crystallizes in the triclinic space group , a=7.931(2) Å, b=7.974(2) Å, c=7.991(2) Å, α=106.99(2)°, β=101.83(2)°, γ=119.28(2)° Z=1, R=0.0280 for 1489 observed reflections. A similar compound, dilithium N,N′-dimethylpiperazinium(2+) selenate tetrahydrate crystallizes in a monoclinic system with space group P2₁/c and lattice parameters a=7.338(1) Å, b=8.792(2) Å, c=12.856(1) Å, β=92.04(2)°, Z=2, R=0.0334 for 1462 observed reflections. Both structures are centrosymmetric with center of symmetry in the center of eight membered ring formed with two SeO₄ tetrahedra and two LiO₄ tetrahedra connected through tops. The two remaining oxygens on each Li atom come from water molecules. The FTIR and FT Raman spectra of both natural and N,O-deuterated substances have been measured and studied. The thermoanalytical properties were studied using TG, DTG and DTA methods in the temperature range 293–873 K for piperazinium derivative and in the range 293–523 K for dimethylpiperazinium derivative. DSC measurements were carried out in the temperature range 95–343 K. No phase transition was found in this temperature region for either of the compounds.     

Quantum chemical study of the transformation of 2-(N-alkylamino)-3-(indol-1-yl)-and 2-(N-alkylamino)-3-(indol-3-yl)maleimides by protic acids: Tandem hydride transfer/cyclization mechanism

The geometric parameters, the charge distribution, and the energetics of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides and their conjugated acids were studied by density functional theory calculations at the B3LYP/6-31G(d) level. The mechanism of the tandem hydride transfer/cyclization sequence, which occurs after protonation of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides, was analyzed. The investigation of the potential energy surface for the tandem hydride transfer/cyclization of the iminium cation that formed upon protonation revealed that the hydride transfer followed by intramolecular cyclization at position 7 of the indole fragment in N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)maleimide is the preferable process, unlike alternative intramolecular cyclization involving the cationic center at the C(2) atom of the indole fragment and the benzene ring of the N-ethylaniline fragment of the indoleninium cation in N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimide. A study of the key intermediates of the assumed reaction mechanism demonstrated that these intermediates are actually stationary points on the potential energy surface (minima and transition states). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2069–2073, December, 2006.     

Radiation grafting of pH and thermosensitive N-isopropylacrylamide and acrylic acid onto PTFE films by two-steps process

Polytetrafluoroethylene (PTFE) was grafted (g) with acrylic acid (AAc) by γ-ray pre-irradiation method to get PTFE-g-AAc films, then N-isopropylacrylamide (NIPAAm) was grafted onto PTFE-g-AAc films with γ-ray to get (PTFE-g-AAc)-g-NIPAAm. PTFE films were irradiated in air at a dose rate of 3.0 kGy h^–1 and different radiation dose. The irradiated films were placed in glass ampoules, which contained aqueous solutions with different monomer concentration (AAc), and then they were heated at different temperatures and reaction time. NIPAAm onto PTFE-g-AAc was carried out with the same procedure with monomer concentration of 1 mol L⁻¹. The thermosensitivity of the samples was defined and calculated as the ratio of the grafted samples swelling at 28 and 35 °C, and pH sensitivity defined as the ratio of the grafted samples swelling at pH 2 and 8.     

New ionic liquid for inorganic cations analysis by capillary electrophoresis: 2-hydroxy- N , N , N -trimethyl-1-phenylethanaminium bis(trifluoromethylsulfonyl)imide (phenylcholine NTf2)

The potentialities of new ionic liquids (ILs) based on choline were evaluated as an electrophoretic medium in capillary electrophoresis for the analysis of alkaline and alkaline earth cations (Li⁺, K⁺, Na⁺, Cs⁺, Mg²⁺, Ba²⁺, Ca²⁺, and Sr²⁺) with indirect UV detection. Two types of capillaries were tested: an untreated fused silica and fused silica coated with a film of polyvinylalcohol. The coated capillary proved to be the best adapted for the metal ions studied. Moreover, it appeared that the nature of the ionic liquid anion influenced the baseline stability, and the bis(trifluoromethylsulfonyl) imide (NTf₂ ⁻) anion seemed to be the most efficient. These preliminary studies led us to synthesize a new ionic liquid, 2-hydroxy-N,N,N-trimethyl-1-phenylethanaminium NTf₂ (phenylcholine NTf₂). This liquid was able to act as the running electrolyte and probe, generating the background signal in indirect UV light and consequently simplifying the electrophoretic medium. Excellent baseline stability, good reproducibility, as well as good sensitivity of detection were obtained with this new ionic liquid. Thus, 510,000 plates/meter for Li⁺ with 40 mM IL were successfully obtained. The optimal concentration of IL was 20 mM with a detection limit ranging from 28 μg L⁻¹ for Li⁺ to 1,000 μg L⁻¹ for Cs⁺. This method (phenylcholine NTf₂ with polyvinylalcohol capillary) was applied to analyze different commercial source and mineral waters. Finally, the potentiality of this ionic liquid in nonaqueous capillary electrophoresis was explored. The use of phenylcholine NTf₂ with a fused silica capillary, in pure methanol medium and in the presence of acetic acid, made it possible to obtain separation selectivity different from that obtained in aqueous medium.     

Chiral recognition and enantiomer assays of N-(3,5-dinitrobenzoyl)amino acid derivatives using electrospray ionization–mass spectrometry

A pair of pseudoenantiomers, anilide derivatives of N-pivaloylproline were prepared and used as chiral selectors for enantiomer discrimination of amides or esters of N-(3,5-dinitrobenzoyl)amino acids in single-stage electrospray ionization/mass spectrometric experiments. Addition of a chiral analyte to a solution of the two pseudoenantiomeric chiral selectors affords selector–analyte complexes in the electrospray ionization mass spectrum where the ratio of these complexes is dependent on the enantiomeric composition of the analyte. The relationship between the ratio of the selector–analyte complexes in the electrospray ionization mass spectrum and the enantiomeric composition of the analyte can be used to relate the extent of the measured enantioselectivity and for quantitative enantiomeric composition determinations. Effects of the added cationic ions (H⁺, Li⁺, Na⁺ and K⁺) and instrument conditions on the selector–analyte ion intensity and the enantioselectivity (α_MS) were investigated. The percent ratio of the sum of the selector–analyte ion counts and the total ion counts decreases accordingly with the increase of the desolvation temperature for H⁺, Na⁺ and K⁺. The ratio for Li⁺ kept almost constant. The best α_MS was observed at a desolvation temperature of 200 °C with the added H⁺. The cone voltage has little effects on the α_MS values though the intensities of selector–analyte complexes are decreased at higher cone voltages. The observed MS enantioselectivities are comparable to the HPLC enantioselectivities and the sense of chiral recognition by MS is consistent with what is observed chromatographically. Quantitative enantiomeric composition determinations for five different samples of N-(3,5-dinitrobenzoyl)leucinyl butylamide at four different concentrations were performed. The average % difference between the HPLC and MS enantiomer determinations is 6.8% and 3.7% for the calibration lines constructed at a concentration of the analyte of 125 μM and 12.5 μM, respectively.     

DFT Study on Intermolecular Cleavage Reaction of N-（2-Hydroxyphenyl）-phthalamic Acid

The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and products were optimized at the B3LYP/6-31G（d, p） level. Vibration analysis was carried out to confirm its identity as transitions＇ structure, and the intrinsic reaction coordinate method（IRC） was used to search the minimum energy path. Two possible reaction channels are reported in this article. The calculated results indicate that O-cyclization reaction channel has the lower activation barrier, and therefore, it occurs more easier than the other.     

B-frame supported bimetallics. [(PMe2ph)2PtB9H11Ru(η-PrC6H4Me)] and [(PMe2ph)2PtB9H9Ru(η-PrC6H4Me)]; an interesting pair of electron-deficient nido and closo geometries

[7,7-(PMe₂Ph)₂-9-(η⁶-^isoPrC₆H₄Me)-7,9-PtRuB₉H₁₁] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-(η⁶-^isoPrC₆H₄Me)-4,4-(PMe₂Ph)₂-1-4-RuPtB₉H₉], which does have a closo geometry, has a formal sub-closo cluster electron count; both compounds are formed in the reaction between [6-(η⁶-^isoPrC₆H₄Me)-nido-6 RuB₉H₁₃], KH and [PtCl₂(PMe₂Ph)₂].     

Synthesis and properties of photoacylotropic (2Z)-2-(N-acyl-N-arylaminomethylidene)benzo[b]thiophen-3(2H)-ones with a chiral migrating group

New photochromic (2Z)-2-(N-acyl-N-arylaminomethylidene)benzo[b]thiophen-3(2H)-ones containing L-amino acid derivatives as migrating groups were synthesized. Light irradiation of their solutions at 436 nm leads to the photoinduced acylotropic rearrangement N → O accompanied by migration of the chiral fragment. The bulky N-acyl group causes steric strain thus destabilizing the amide form of compounds and facilitating the photorearrangement. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2690–2696, December, 2005.     

Co(III) complexes of Me-salpn and Me-salbn and the ring size effect on the coordination modes and electrochemical properties: The crystal structures of trans-[Co(Me-salpn)(py)2]PF6 and cis-α-[Co(Me-salbn)(4-Mepy)2]BPh4 · 4-Mepy

The synthesis and characterization of a series of cobalt(III) complexes of the general type [Co(N₂O₂)(L₂)]⁺ are described. The N₂O₂ Schiff base ligands used are Me-salpn (H₂Me-salpn = N,N′-bis(methylsalicylidene)-1,3-propylenediamine) (1–3) and Me-salbn (H₂Me-salbn = N,N′-bis(methylsalicylidene)-1,4-butylenediamine) (4–5). The two ancillary ligands L include: pyridine (py) 1, 3-metheylpyridine (3-Mepy) 2, 1-methylimidazole (1-MeIm) 3, 4-methylpyridine (4-Mepy) 4 and pyridine (py) 5. These complexes have been characterized by elemental analyses, IR, UV–Vis, and ¹H NMR spectroscopy. The crystal structures of trans-[Co^III(Me-salpn)(py)₂]PF₆, 1, and cis-α-[Co^III(Me-salbn)(4-Mepy)₂]BPh₄ · 4-Mepy, 4, have been determined by X-ray diffraction. Examination of the solution and crystalline structures revealed that the outer coordination sphere of the complexes exerts a noticeable influence on the inner coordination sphere of the Co(III) ion. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Co^III–Co^II is electrochemically irreversible, which is accompanied by the dissociation of the axial (R-py)–cobalt bonds. It has also been observed that the Co(III) state is stabilized with increasing the flexibility of the ligand environment.     

Synthesis and catalytic properties in olefin epoxidation of dioxomolybdenum(vi) complexes bearing a bidentate or tetradentate salen-type ligand

The monomeric cis-dioxomolybdenum(VI) complexes [MoO₂(oep-saldpen)] and [MoO₂Cl₂(oep-H₂saldpen)], with a tetradentate [N₂(imine)O₂] and bidentate [N₂(imine)] salen-type ligand functionalised with two pyrrole derivative pendant arms [oep-H₂saldpen = 1,2-diphenylethylenebis(3-oxyethylpyrrole)salicylideneimine], were synthesised and characterised by ¹H NMR, IR and Raman spectroscopy. The solid-state structure of the free ligand oep-H₂saldpen was determined by single crystal X-ray diffraction. Assignment of the vibrational spectra of the molybdenum complexes was supported by carrying out ab initio calculations for the possible isomers using [MoO₂(salen)] and [MoO₂Cl₂(H₂salen)] as model compounds [H₂salen = N,N′-ethylenebis(salicylideneimine)]. The oep-saldpen complexes were examined as catalysts for the epoxidation of cyclooctene, (R)-(+)-limonene, styrene, α-pinene, and cis and trans-β-methylstyrene, with tert-butyl hydroperoxide as the oxidant. Both complexes exhibited high selectivity for the epoxidation reaction, with the bis(chloro) complex being always the more active of the two.