Hetarylamidines derived from PtIV-mediated coupling of nitriles with aminoheterocycles

The trans-[PtCl₄(EtCN)₂] complex is involved in coupling reactions (CH₂Cl₂, 30–35 °C, 10–15 min) with 2-amino derivatives of heterocyclic compounds (2-NH₂Het, where Het is pyridyl, 4-methylpyridyl, 5-methylpyridyl, 6-methylpyridyl, or thiazolyl) to form the trans-[PtCl₄{ N(H)=C(Et)NHHet}₂] complexes (1–5) with κ¹(N)-coordinated hetarylamidine ligands. The reaction with the use of 2-aminopyrimidine (2-NH₂Pym) produces the [PtCl₄(₂-NH₂Pym)₂] complex (6) as a result of complete replacement of the nitrile ligands in the [PtCl₄(EtCN)₂] complex. The compositions and structures of compounds 1–6 were confirmed by elemental analysis (C, H, N), IR spectroscopy, ¹H, ¹³C{1H}, and ¹⁹⁵Pt{¹H} NMR spectroscopy, and FAB mass spectrometry. Complex 1 was additionally characterized by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1572–1576, September, 2006.     

Syntheses of Aladan and [Ald^6]loloatin C and Study on Their Fluorescent Properties

Aladan {β-[6＇-（N,N-dimethyl）amino-2＇-naphthoyl]alanine} and aladan-containing cyclodecapeptide [Ald^6]loloatin C were synthesized. The properties of their fluorescent behaviours both in aqueous buffer and micelles created by sodium dodecylsulfate （SDS） and dodecylphosphorylcholine （DPC） were further investigated. It was found that in either of micelle systems, [Ald^6]loloatin C possesses red-shift emission maximum wavelength and higher quantum yield. This property could be useful in the research of peptide-cell membrane interaction.     

Synthesis and characterization of 2-phenylaniline cyclopalladated complexes

Reaction of the dinuclear complex [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl]₂ (1) with ligands (L = 4-picoline, sym-collidine) gave the six-membered palladacycles [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (2). The complex 1 reacted with AgX (X = CF₃SO₃, BF₄) and bidentate ligands [L–L = phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), bipy(2,2′-bipyridine) and dppp (bis(diphenylphosphino)propane)] giving the mononuclear orthopalladated complexes [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}(L–L)] (3) [L–L = phen, dppe, bipy and dppp]. These compounds were characterized by physico-chemical methods, and the structure of [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (L = sym-collidine) was determined by single-crystal X-ray analysis.     

Oxygen- versus carbon-coordination of the alpha-stabilized phosphorus ylide Ph<Subscript>3</Subscript>P=C(H)R in palladacycles bearing secondary amines

The ortho-metalated complex [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)₂ and secondary benzylamine [a, EtNHCH₂Ph; b, t-BuNHCH₂Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph₃P=C(H)COC₆H₄-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C₆H₄C=CHPPh₃){κ ² (C,N)-[C₆H₄CH₂NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques.     

Different coordination modes of the dimethyldisulfide ligand in trimethylplatinum(IV) complexes

The reaction of [PtMe₃(bpy)(Me₂CO)](BF₄) (2) (prepared from [PtMe₃I(bpy)] (1) plus Ag(BF₄)) with MeSSMe resulted in the formation of [PtMe₃(bpy)(MeSSMe-κS)](BF₄) (3). A single-crystal X-ray diffraction analysis revealed in the octahedral Pt(IV) complex (configuration index: OC-6-33), a conformation of the monodentately κS bound MeSSMe ligand (C–S–S–C 92.7(4)°) being very close to that in non-coordinated MeSSMe, thus allowing some hyperconjugative interaction stabilizing the S–S bond. The reaction of [K(18C6)][(PtMe₃)₂(μ-I)(μ-pz)₂] (4; 18C6 = 18-crown-6, Hpz = pyrazole) with Ag(BF₄) and MeSSMe resulted in the formation of dinuclear complexes [(PtMe₃)₂(μ-pz)₂(μ-MeSSMe)] existing at room temperature in acetone solution as different fast interconverting isomers. At –40 °C, two isomers with a μ-1κS:2κS (5a) and a μ-1κS:2κS′ (5b) coordinated MeSSMe ligand in the ratio 2:1 could be identified ¹H NMR spectroscopically. DFT calculations of type 5 complexes revealed the existence of two conformers with a μ-MeSSMe-1κS:2κS ligand, which differ mainly in the C–S–S–C dihedral angle (66.4 vs. 180.0° 6a/6a′). They have essentially the same energy and a very low activation barrier in acetone as solvent (1.3 kcal/mol) for their mutual interconversion. A further equilibrium structure was identified to be an isomer having a μ-MeSSMe-1κS:2κS′ ligand (6b) that proved to be only 1.9 kcal/mol higher in energy than 6a/6a′.     

Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

The mannich reaction in the synthesis of N,S-containing heterocycles 4. Aminomethylation of 6-amino-3,5-dicyano-1,4-dihydropyridine-2-thiolates: A convenient regioselective route to 3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene derivatives

Treatment of N-methylmorpholinium 4-R-6-amino-3,5-dicyano-1,4-dihydropyridine-2-thiolates (R = 2-ClC₆H₄ and 2-MeOC₆H₄) with primary amines in the presence of an excess of formaldehyde gave 13-R-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene-1,9-dicarbonitrile derivatives in high yields (66–95%). In a similar way, aminomethylation of 3-R-10-amino-7,11-dicyano-9-aza-3-azoniaspiro[5.5]undeca-7,10-diene-8-thiolates (R = Me and Et) afforded 1′-alkyl-8-thioxospiro[3,5,7,11-tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene-13,4′-piperidine]-1,9-dicarbonitriles in 43–91% yields. Alternatively, these compounds were obtained by multicomponent cyclocondensation of N-alkylpiperidin-4-ones, cyanothioacetamide, primary amines, and aqueous formaldehyde. The starting 3-R-10-amino-7,11-dicyano-9-aza-3-azoniaspiro[5.5]undeca-7,10-diene-8-thiolates were prepared by a new method from N-alkylpiperidin-4-ones and cyanothioacetamide. The structure of 5,11-bis(4-ethoxyphenyl)-13-(2-methoxyphenyl)-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene-1,9-dicarbonitrile was examined by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1014–1022, May, 2007.     

Palladium(II) complexes with R2edda-derived ligands. Part V. Reaction of O,O′-diethyl-(S,S)-ethylenediamine-N,N′-di-2-(3-methyl)butanoate with K2[PdCl4]

The reaction of K₂[PdCl₄] with [(S,S)-H₂(Et)₂eddv]Cl₂ diester (O,O′-diethyl-(S,S)-ethylenediamine-N,N′-di-2-(3-methyl)butanoate) (1) resulted in [PdCl₂{(S,S)-(Et)eddv-κ² N,N′,κO}] (2) complex with one hydrolyzed ester group. The compound was characterized by spectroscopic methods and it was found that the reaction is diastereoselective (¹H and ¹³C NMR; one diastereoisomer of four possible). In addition, the structure of 2 was confirmed by X-ray diffraction analysis, indicating that the product is the (R,R)–N,N′-configured isomer. DFT calculations support the formation of one diastereoisomer of 2.     

Intensity-tunable micelles and films containing bimetal ions—europium(III) and terbium(III)

In this paper, multicolored micelles were prepared by coordination of lanthanide(III) (europium(III) (Eu(III)) and terbium(III) (Tb(III))) ions with block copolymer in different molar ratios of n _Eu(III)/n _Tb(III). The micelles formed by polymer–Eu(III)/Tb(III) could emit higher quantum yield luminescence than the mixture of polymer–Eu(III) micelles and polymer–Tb(III) micelles. The micelles containing Eu(III) and Tb(III) could emit a yellow-green color, and the intensity varied with the molar ratios of n _Eu(III)/n _Tb(III). In the constant concentrations of Eu(III) and 1,10-phenanthroline (Phen), the intensity of ⁵D₀→⁷F₂ increased with the addition of Tb(III), and the intensity of ⁵D₄→⁷F₅ decreased with the increasing of Eu(III) in the constant concentrations of Tb(III) and Phen. All the multicolored micelles could be spin-coated as intensity-tunable films.     

Experimental and DFT Studies on the DNA-binding Properties of Ruthenium(II) Complexes [Ru(phen)2L]2+(L = o-MOP, o-MP, o-CP and o-NP)

A series of ruthenium(II) complexes with electron-donor or electron-acceptor groups in intercalative ligands, [Ru(phen)₂(o-MOP)]²⁺ (1), [Ru(phen)₂(o-MP)]²⁺ (2), [Ru(phen)₂(o-CP)]²⁺ (3) and [Ru(phen)₂(o-NP)]²⁺ (4), have been synthesized and characterized by elementary analysis, ES-MS, ¹H NMR, electronic absorption and emission spectra. The binding properties of these complexes to CT-DNA have been investigated by spectroscopy and viscosity experiments. The results showed that these complexes bind to DNA in intercalation mode and their intrinsic binding constants (K_b) are 1.1, 0.35, 0.53 and 1.7 × 10⁵ M⁻¹, respectively. The subtle but detectable differences occurred in the DNA-binding properties of these complexes are mainly ascribed to the electron-withdrawing abilities of substituents (–OCH₃ < –CH₃ < –Cl < –NO₂) on the intercalative ligands as well as the intramolecular H-bond (for substituent –OCH₃) which increase the planarity area of the intercalative ligand to some extent. The density functional theory (DFT) calculations were also performed and used to further discuss the trend in the DNA-binding affinities of these complexes.     

Organometallic gold(I)–nickel(II)–aryldiethynyl (–C≡C(Ar)C≡C–) phosphine complexes: synthesis and multinuclear n.m.r. study

Silver triflate [AgOTf] assisted de-bromination gives [Ni(dppm/dppe/(PPh₃)₂)(OTf)₂], which on reaction with aryldiethynyls and gold(I) phosphines in CH₂Cl₂ medium, by the self assembly technique, leads to [{Ni(dppm/dppe/(PPh₃)₂}{(1,4-AB)Au(PPh₃)}₂] [{Ni₄(dppm/dppe/(PPh₃)₂)₄(1,4AB)₄}] [dppm/dppe = diphenyl phosphino-methane (1), -ethane (2), where OSO₂CF₃ is the triflate anion]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum. I.r. spectra of the complexes show –C=C– and –C=N–, as well as phosphine stretching. The ¹H-n.m.r. spectra as well as ³¹P(¹H)-n.m.r. suggest solution stereochemistry, proton movement, phosphorus proton interaction. Considering all the moities there are a lot of carbon atoms in the molecule reflected by the ¹³C-n.m.r. spectrum. In the ¹H–¹H-COSY spectrum of the present complexes and contour peaks in the ¹H–¹³C-HMQC spectrum, assign the solution structure and stereo-retentive transformation in each step.     

An electroconductivity study on degree of counterion binding or dissociation of a-sulfonatomyristic acid methyl ester micelles in water as a function of temperature

 For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, the differential conductivity (∂κ/∂C) _T , _P vs. square root of concentration (√C) was employed in order to determine not only CMC but also the limiting molar conductance (Λ⁰) and the molar conductance of micellar species (Λ^M). Based on the data of the degree of counterion binding to micelles (β) determined previously at different temperatures ranging 15–50 °C at every 5 °C, the experimental values of the degree of dissociation (ionization) of a micelle (α_EX) were calculated by regarding as α_EX=1−β. The ratio Λ^M/Λ⁰ corresponding to the ratio of slopes below and above CMC in the curve of specific conductivity (κ) vs. concentration (C), which has been often assumed to be the degree of ionization of micelles (α), was compared with the present α_EX. However, the ratio Λ^M/Λ⁰ (=α) was found to have a correlationship with α_EX (=1−β) as α_EX≈0.40×(Λ^M/Λ⁰), or strictly, α_EX=0.40 (Λ^M/Λ⁰)+0.08, indicating that the simple ratio of the slopes below and above CMC in κ vs. C curve is not true for α_EX=1−β. On the other hand, the method proposed by Evans gave a value closer to α_EX compared with the simple ratio. Received: 17 September 1996 Accepted: 8 April 1997     

Mechanistic investigation of oxidation of a diketone by bromamine-B in acid medium

Oxidation of acetylacetone (AA) by bromamine-B (BAB) in HC1 medium (0.1 to 0.6 mol dm⁻³) at constant ionic strength has been investigated at 40°C. The rate is first order in [BAB]₀ and fractional order each in [AA]₀ and [H⁺]. The reaction is also catalysed by chloride ion. Michaelis-Menten type of kinetics is observed. Decrease in dielectric constant of medium increases the rate. A solvent isotope effect κ′H₂O/κ′D₂O = 0.96 has been noted. Activation parameters for the rate limiting step have been computed. The mechanism involves the enol form of the diketone.     

Red electrophosphorescent platinum(II) quinolinolate complexes

Abstract  

Luminescent organoplatinum complexes featuring 8-quinolinolates as chelating ligands have been synthesized and characterized. Substitution of the quinolinolate ligand has been achieved in the 5 position, where benzoyl substituents were introduced by reacting 8-hydroxyquinoline and the corresponding benzoyl chloride in a Friedel–Crafts acylation. The resulting complexes, κ²(N,C²)-(2-(4-tert-butylphenyl)pyridine)-κ²(N,O)-(5-(4-tert-butylphenyl)(8-quinolinolato-5-yl)methanone)platinum(II) and κ²(N,C²)-(3-hexyloxy-2-phenylpyridine)-κ²(N,O)-((8-quinolinolato-5-yl)phenylmethanone)platinum(II), have been investigated by nuclear magnetic resonance and infrared spectroscopy, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, X-ray analysis, thermal analysis, cyclic voltammetry, UV–vis absorption spectroscopy, and luminescence measurements in solution and in the solid state. The solid-state structures of the complexes were found to be dominated by π–π intermolecular interactions. Organic light-emitting devices based on the complexes and a matching host material gave red to near-infrared electroluminescence with low-onset voltages (4–5 V) and continuous wave luminance intensities exceeding 500 cd/m².     

Syntheses,molecular structures and magnetic properties of two hybrid organic–inorganic salts of bis(maleonitriledithiolato)copper(II) and substituted benzyl-4-dimethylaminopyridinium cations

Two new hybrid organic–inorganic salts, [BzDMAP]₂[Cu(mnt)₂](1) and [NO₂BzDMAP]₂[Cu(mnt)₂] (2) ([BzDMAP]⁺ = 1-benzyl-4′-dimethylaminopyridinium, [NO₂BzDMAP]⁺ = 1-(4′-nitrobenzyl)-4′-dimethylaminopyridinium, and mnt²⁻ = maleonitriledithiolate) have been characterized structurally and magnetically. The [BzDMAP]⁺ or [NO₂BzDMAP]⁺ cations (C) and the [Cu(mnt)₂]²⁻ anions (A) in 1 and 2 stack into a 1D alternating CC-A-CC-A-CC column. The Cu···N, π···π, C–H···N, C–H···O, and C–H···S weak interactions play important roles in the molecular stacking and generate a 2D or 3D structure of 1 and 2. The magnetic susceptibilities of these salts measured in the temperature range 2.0–300 K show weak antiferromagnetic coupling features with θ = −2.370 K for 1 and −0.222 K for 2.     

Solvent/substrate effects on the micelle-catalyzed aquation reactions of some iron(II) phenanthroline complexes, I. Influence of water and acid on the aquation of Fe(Ph2Phen)32+ in acetone

The effects of a substrate additive, H⁺ and solvents (water and acetone), on the micelle-catalyzed aquation of tris-(4,7-diphenyl-1, 10-phenanthroline)iron(II), Fe(Ph₂Phen)₃ ²⁺, have been investigated using^#Triton X-100 micelles. The k₀ vs. [TX-100] profiles at fixed [H₂O] are structured, exhibiting maxima. Catalytic factors of 46.6–171.7 are observed for 5.56×10⁻²≤[H₂O] 55.60×10⁻² mol dm⁻³. On the other hand, at fixed [H⁺], the k₀ vs. [TX-100] exhibit broad maxima. The aquation reaction is inhibited by H⁺ and catalytic factors decrease rapidly and exponentially from 422.5 to 20.9 for 0.20×10⁻³≤[H⁺]≤2.00×10⁻³ mol dm⁻³. The aquation is found to be faster (ca. 160–1200 fold) in acetone than in the aqueous medium depending on the added [H₂O]. These observations are rationalized on the basis of a proposed modified lamellar structure for the Triton X-100 (TX-100) micelles in which direct substitution of water molecules into the coordination sphere of the complex occurs.     

Structure of water-glycine solutions in saturated and near-saturated regions according to compressibility data

Ultrasonic velocity and density values are measured for aqueous solutions containing 2.00 mol.%, 4.00 mol.%, and 5.00 mol.% glycine in a temperature range of 15–65°C, 5.50 mol.% glycine (20–65°C), and 6.00 mol.% glycine (25–65°C). Adiabatic compressibilities (κ_S) and molar adiabatic compressibilities (K_S) are calculated. The values of κ_S and K_S decrease monotonically with an increase in glycine concentrations up to saturation at all the temperatures. The temperature dependences of κ_S and κ_S have minima that are typical of water and aqueous solutions; the positions of the minima depend on the glycine concentration. The temperature coefficients of the molar compressibility, ∂K_S/∂T, change their signs from negative to positive at lower temperatures (by approximately 10 deg) than ∂κ_S/∂T.     

Multinuclear NMR investigation on organometallic gold(III) pentafluorophenylarylazoimidazole complexes

Reaction of [Au(C₆F₅)(tht)₂Cl](OTf) with RaaiR′ in CH₂Cl₂ medium leads to [Au(C₆F₅)(RaaiR′)Cl](OTf) [RaaiR′ = p-R–C₆H₄–N=N–C₃H₂–NN-1-R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), tht is tetrahydrothiophen]. The maximum molecular peak of [Au(C₆F₅)(MeaaiMe)Cl] is observed at m/z 599.51 (100 %) in the FAB mass spectrum. Ir spectra of the complexes show –C=N– and –N=N– stretching near at 1590 and 1370 cm⁻¹ and near at 1510, 955, 800 cm⁻¹ due to the presence of pentafluorophenyl ring. The ¹H-NMR spectral measurements suggest methylene, –CH₂–, in RaaiEt gives a complex AB type multiplet while in RaaiCH₂Ph shows AB type quartets. ¹³C-NMR spectrum of complexes confirm the molecular skeleton. In the ¹H-¹H-COSY spectrum as well as contour peaks in the ¹H-¹³C HMQC spectrum for the present complexes, assign the solution structure and stereoretentive conformation. The electrochemistry gives the ligand reduction peaks.     

Competition Between O2 and H2O2 in the Oxidation of Fe(II) in Natural Waters

The oxidation rates of nanomolar levels of Fe(II) in seawater (salinity S = 36.2) by mixtures of O₂ and H₂O₂ has been measured as a function of pH (5.8–8.4) and temperature (3–35∘C). A competition exists for the oxidation of Fe(II) in the presence of both O₂ (μ mol⋅L⁻¹ levels) and H₂O₂ (nmol⋅L⁻¹ levels). A kinetic model has been applied to explain the experimental results that considers the interactions of Fe(II) with the major ions in seawater. In the presence of both oxidants, the hydrolyzed Fe(II) species dominate the Fe(II) oxidation process between pH 6 and 8.5. Over pH range 6.2–7.9, the FeOH⁺ species are the most active, whereas above pH 7.9, the Fe(OH)⁰₂ species are the most active at the levels of CO²⁻₃ concentration present in seawater. The predicted Fe(II) oxidation rate at [Fe(II)]₀ = 30nmol⋅L⁻¹ and pH = 8.17 in the oxygen-saturated seawater with [H₂O₂]₀ = 50nmol⋅L⁻¹ (log ₁₀ k = −2.24s⁻¹) is in excellent agreement with the experimental value of log ₁₀ k = −2.29s⁻¹ ([H₂O₂]₀ = 55nmol⋅L⁻¹, pH = 8).     

Gold(I)-diphenylphosphinomethane–arylazoimidazole: synthesis and multinuclear NMR investigation

Reaction of [Au₂(dppm)Cl₂] with AgOTf in CH₂Cl₂ medium followed ligand addition and leads to [Au₂(dppm)(RaaiR′)](OTf) [RaaiR′ = p-R–C₆H₄–N = N–C₃H₂–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion, and dppm is the diphenylphosphinomethane-ring]. The ¹H-n.m.r. spectral measurements suggest methylene, –CH₂–, in RaaiEt gives a complex AB type multiplet while in RaaiCH₂Ph it shows AB type quartets with coupling constant of avg. 6 Hz. Considering all the moities there are a lot of different carbon atoms in the molecule which gives a lot of different peaks in the ¹³C-n.m.r spectrum. In the ¹H–¹H-COSY spectrum of the present complexes and contour peaks in the ¹H–¹³C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive transformation in each step.