Structural and electrochemical studies of novel bis(mu-methoxo)diiron complexes: observation of Fe(III)Fe(IV) and Fe(IV)Fe(IV) states resonating with phenoxyl radicals

Novel diiron complexes with an Fe2(mu-OMe)2 core were studied as models of the active site of nonheme iron-containing enzymes. X-ray crystal structures of the complexes showed the existence of two types of ligand folding-parallel and twisted-both of which have four virtually equivalent phenolato groups sticking out from the Fe2O2 rhombic plane. Cyclic voltammetry measurements revealed two or more distinct redox waves in a region of relatively high potential, in addition to known Fe(II)/Fe(III) redox waves in a region of lower potential. These new peaks were assigned to the high-valence state of iron atoms, that is, Fe(III)Fe(IV) and Fe(IV)Fe(IV), resonating with the phenoxyl radical(s). The split width of the redox waves ranged from 0.14 to 0.20 eV, which may be a measure of the electronic interaction of the phenolate groups through the Fe2(mu-OMe)2 core.     

Basicity of 2-phenyl-5-R-1,3,4-oxadiazoles

We have studied the basicity of 2-phenyl-5-R-1,3,4-oxadiazoles (R = H, Me, CH₂Ph, t-Bu, CH₂Cl, CCl₃, CF₃) in aqueous sulfuric acid solutions. These compounds are weak organic bases (pK_BH ⁺ is −1.8 to −5.2). The values of pK_BH ⁺ determined on the H₀ and X acidity function scales agree well with each other. The substituent at the 5 position has a substantial effect on the basicity of the 1,3,4-oxadiazole ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 748–756, May, 2006.     

Syntheses,Characterization and Crystal Structures of Three Structurally Similar Dinuclear Schiff Base Cadmium(II) Complexes with Bridging Azide or Thiocyanate Ligands

Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N₃) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd₂(L1)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd₂(L2)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd₂(L3)₂(NCS)₂(μ_1,3‐NCS)₂] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures.     

Electrochemical synthesis of Co,Ni, and Zn complexes with 2-Pyrrole-[N-(o-hydroxyphenyl)methylimines]: The crystal structure of 2,2′-Bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II)

The electrochemical oxidation of anodic cobalt, nickel, and zinc in acetonitrile containing both 2-pyrrole-[N-(o-hydroxyphenyl)methylimines] (H₂L) and a bidentate ligand (1, 10-phenanthroline(phen) or 2,2′-bipyridine(bipy)) yielded compounds of general formula M(HL)₂ · phen and M(HL)₂ · bipy (M = Co, Ni, Zn). The crystal structure of 2,2′-bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II) was determined by X-ray diffraction. This compound crystallizes in the orthorhombic space group Pccn with a = 19.430(2), b = 28.488(2), c = 17.567(1) Å. The nickel atom has a distorted octahedral geometry, and the pyrrole nitrogen is not coordinated. The IR, ¹H-NMR and UV-visible spectra of the complexes are discussed and related to the structure.     

Water as an efficient medium for the synthesis of tetrahydro-β-carbolines via Pictet-Spengler reactions

A mild and efficient protocol for the Pictet-Spengler reaction in water using an acid catalyst has been described. The condensation of tryptophan, tryptamine, and N_b-benzyl tryptophan with different aldehydes having both electron-withdrawing and -donating substituents in the presence of a catalytic amount of TFA in water furnished tetrahydro-β-carbolines in good isolated yields. A salient feature of the water mediated Pictet-Spengler reaction was the general trend observed during the condensation of Trp-OMe and aryl/aliphatic aldehydes furnishing diastereomeric mixtures with a preference for the cis-isomer.     

Solvolthermal Syntheses and Crystal Structures of Three Linear Trinuclear Schiff Base Complexes of Zinc(II) and Cadmium(II)

Three linear trinuclear Schiff base complexes, {Zn[Zn(CH₃COO)(C₁₇H₁₆N₂O₂)]₂} ( 1 ), {Zn[Zn(CH₃COO)(C₂₅H₂₀N₂O₂)]₂} ( 2 ), and {Cd[Cd(CH₃COO)(C₁₈H₁₈N₂O₂)]₂} ( 3 ), were synthesized for the first time under solvolthermal conditions. Their structures have been characterized by elemental analyses, X-ray single crystal determinations, and infrared spectroscopy. There are three bridges across the M-M atom pairs (M is Zn for 1 and 2 , or Cd for 3 ) in each complex, involving two O atoms of a Schiff base ligand (N,N′-bis(salicylidene)-1, 3-propanediaminate (SALPD^2-) for 1 , N, N′-bis(2-hydroxy-naphthalmethenylimino)-1, 3-propanediaminate (NAPTPD^2-) for 2 , and N,N′-bis-(salicylidene)-1,4-butanediaminate (SALBD^2-) for 3 ), and an O-C-O moiety of a μ-acetato group. In each of the complexes, the central M²⁺ ion is located on an inversion center and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal M²⁺ ions is irregular square pyramidal, with two O atoms and two N atoms of the Schiff base ligand in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal M²⁺ ions are mutually trans. The M…M distances are 3.050(3) Å in 1 , 3.139(2) Å in 2 , and 3.287(6) Å in 3 .     

Synthesis of N-Pyridylmethylidene-2-aminopyridines and their Methyl-substituted Derivatives in the Presence of Molecular Sieves

We have studied condensation of 2-, 3-, 4-pyridinealdehydes and 6-methylpyridine-2-aldehyde with 2-aminopyridine and its 3-, 4-, and 6-methyl derivatives in benzene in the presence of molecular sieves. The reactions occur even at room temperature to form the corresponding pyridyl-pyridyl azomethines, and also aminals. We have determined the optimal conditions for carrying out the processes with the aim of obtaining both types of products. We consider the characteristics of the mass spectra for the synthesized aldimines. We present the X-ray diffraction results for the two aminals.     

Synthesis and properties of the first stable silylene-isocyanide complexes

The first stable silylene-isocyanide complexes, [Tbt(Mes)SiCNAr] (5 c: Ar=Tip, 5 d: Ar=Tbt, 5 e: Ar=Mes*; Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes=mesityl, Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) were successfully synthesized by the reaction of a kinetically stabilized disilene, [Tbt(Mes)Si=Si(Mes)Tbt] (1), with bulky isocyanides, ArNC (3c-e). The spectroscopic data of 5 c-e and theoretical calculations for a model molecule indicated that 5 c-e are not classical cumulative compounds but the first stable silylene-Lewis base complexes. The reactions of 5 c-e with triethylsilane and 1,3-dienes gave the corresponding silylene adducts, and they underwent isocyanide-exchange reactions in the presence of another isocyanide at room temperature. These results indicate dissociation of complexes 5 c-e to the corresponding silylene 2 and isocyanides 3 c-e under very mild conditions. The reaction of 5 c with methanol gave the MeOH adduct 16, [Tbt(Mes)SiHC(OMe)NTip], which has a hydrogen atom on the silicon atom. This regioselectivity can be explained in terms of the contribution of zwitterionic resonance structures D and E, which have an anion on the silicon atom. This result indicates that 5 c is not a classical cumulene having Si=C double bonds that should react with methanol to give adducts bearing a methoxyl group on the silicon atom. Although the reactions of 5 c-e with electrophilic reagents such as methanol, hydrogen chloride, and methyl iodide gave the formal silylene adducts, the studies on the reaction mechanism by trapping experiments and the observation of the intermediate suggested that the reaction mainly or partially proceeds by initial nucleophilic attack of the silicon atom, as is the case in the formation of 16 in the reaction of 5 c with methanol. It was revealed that 5 c-e show the nucleophilicity of the silicon atom, most likely resulting from the contribution of the zwitterionic resonance structures D and E.     

Synthesis, structural characterization and electrochemical study of 1,1′-ferrocenylene labeled amino acids

Unsymmetrical 1,1′-disubstituted ferrocenes bearing an amino acid moiety and a conjugated electron density controlling substituent were synthesized conveniently starting from 1,1′-ferrocenedicarbaldehyde. The novel ferrocene amino acid derivatives were completely characterized from their MS, ¹H NMR and ¹³C NMR spectra. Their electrochemical behavior was studied by cyclic voltammetry. Their formal redox potentials E_f were slightly influenced by the nature of the amino acid and mainly by the kind of the ethenyl substituent. Furthermore all the (Z)-isomers exhibited a slight anodic shift compared with the corresponding (E)-isomers.     

Stoichiometric and catalytic methods of asymmetric synthesis of nonproteinogenic α-and β-amino acids via transition metal coordination compounds

The complexes of glycine, -alanine, and -alanine with (S)-[N-(N-benzylprolyl)amino] benzophenone formed by Ni(II) and Cu(II) ions and Schiff bases enter into different nucleophilic and electrophilic reactions with the formation of diastereoisomeric complexes which decompose into proteinogenic and nonproteinogenic L-amino acids with a high chemical yield and elevated optical purity (70–90%). Optically pure amino acids can be obtained from diastereoisomerically pure complexes after the complexes are separated by recrystallization of the mixture of diastereoisomeric complexes formed. A new type of interphase catalysts of C-alkylation of achiral Schiff bases was proposed. The catalysts are positively charged Ni(II) and Cu(II) complexes of Schiff bases of chiral diamines. In some cases, these complexes have a higher activity and capacity to execute asymmetric alkylation than traditional chiral interphase catalysts based on cinchonidine.Based on materials in the section report by Yu. N. Belokon' to the 7th European Symposium on Organic Chemistry, ESOC-7.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1106–1127, May, 1992.