Specific Features of Chlorotropism in the ENC Triad (E = PIV-PVI,C) of High-Coordination Phosphorus Chlorides and Trichloromethyl Isocyanate

The semiempirical MNDO method and its parametrized PM3 version in supermolecular approximation was used for a comparative study of the structure and alternative mechanisms of chlorotropism in the ENC triad (E = P^{I V - V I}, C) of amidinium tetrachlorophosphorate Cl₄P(NCH₃)₂CCCl₃ (I), phosphazopentachloroethane Cl₅C₂NPO₂C₆H₄, (II), trichloromethyl isocyanate Cl₃CNCO (III), and their 1:2 chloroform solvates. The absence of the thermodynamically stable intermediate as a separated ion pair in the chlorotropic transformations of structures I, III and the high enthalpy of the substrate-intermediate transformation for structure II show that the sigmatropic mechanism of chlorotropism in compounds under study is the only probable one. The activation barrier of chlorotropism in phosphorus systems I, II is much reduced. In the case of specific solvation, a weak tendency to further reduction of the activation barrier for structures I-III is observed, and the equilibrium for phosphorus systems I, II, is appreciably shifted, unlike system III, where, according to experimental data, the equilibrium is fully to the side of the carbamoyl isomer Cl₂C = NC(O)Cl.     

Four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives

Crystal structures are reported for four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives, namely (2,2′‐bipyridyl)(ethenyl)(ferrocenyl)boronium hexafluoridophosphate, [Fe(C₅H₅)(C₁₇H₁₅BN₂)]PF₆, (Ib), (2,2′‐bipyridyl)(tert‐butylamino)(ferrocenyl)boronium bromide, [Fe(C₅H₅)(C₁₉H₂₂BN₃)]Br, (IIa), (2,2′‐bipyridyl)(ferrocenyl)(4‐methoxyphenylamino)boronium hexafluoridophosphate acetonitrile hemisolvate, [Fe(C₅H₅)(C₂₂H₂₀BN₃O)]PF₆·0.5CH₃CN, (IIIb), and 1,1′‐bis[(2,2′‐bipyridyl)(cyanomethyl)boronium]ferrocene bis(hexafluoridophosphate), [Fe(C₁₇H₁₄BN₃)₂](PF₆)₂, (IVb). The asymmetric unit of (IIIb) contains two independent cations with very similar conformations. The B atom has a distorted tetrahedral coordination in all four structures. The cyclopentadienyl rings of (Ib), (IIa) and (IIIb) are approximately eclipsed, while a bisecting conformation is found for (IVb). The N—H groups of (IIa) and (IIIb) are shielded by the ferrocenyl and tert‐butyl or phenyl groups and are therefore not involved in hydrogen bonding. The B—N(amine) bond lengths are shortened by delocalization of π‐electrons. In the cations with an amine substituent at boron, the B—N(bipyridyl) bonds are 0.035 (3) Å longer than in the cations with a methylene C atom bonded to boron. A similar lengthening of the B—N(bipyridyl) bonds is found in a survey of related cations with an oxy group attached to the B atom.     

Molecular structure of some [1.1 ]ferrocenylruthenocenophanium (n = 1,2 polyiodides salts

Oxidation of [1.1]ferrocenylruthenocenophane with a large excess and 1.5 equivalents of iodine gives dicationic iodo[1.1]ferrocenylruthenocenophanium²⁺I₃⁻ · 0.5I₂2 (1) and monocationic [1.1]ferrocenylruthenocenophanium⁺I₃⁻ (2) salts respectively. The structures of 1 and 2 were analyzed by single-crystal X-ray diffraction studies. The crystal form of 1 is monoclinic space group C2/c, A = 21.35](5), B = 20.594(5), C = 17.397(4) Å, β = 124.17(1)°, Z = 8, and the final R = 0.068 and R_w = 0.070. The cation formulated as [Fe^III(C₅H₄CH₂C₅H₄)₂Ru^IVI]²⁺ exists in a syn-conformation as in the cases of the neutral compound. The distance between the Ru^IV and Fe^II is 4.656(4) Å, which is much shorter than the value of the neutral compound (4.792(2) Å), and the bond angle of I---Ru^IV,Fe^III is 81.26°. The dihedral angle between the two η⁵-C₅H₄ (fulvenide) rings on the Ru^IV moiety is 37.56° due to the Ru^IV---I bond (2.758(3) Å). These two rings of Fe^III and Ru^IV moieties are essentially eclipsed. The unit cell has three kinds of I₃⁻ (I_3a⁻, I_3b⁻ and I_3c⁻) and one I₂, and the formula of 1 is given as [Fe^III(C₅H₄CH₂CSH₄)₂Ru^IVI]²⁺I₃⁻ · 0.5(I₃⁻)₂ · 0.5I₂. The crystal of 2 formulated as [Fe^III(C₅H₄CH₂C₅H₄)₂Ru^II]⁺I₃⁻ is triclinic space group

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, and the final R = 0.067 and R_w = 0.068. The unit cell has two independent molecules (unit A and B); i.e. two kinds of distance between the Ru^II and Fe^III, are observed; one (A) is 4.615(3) and the other (B) is 4.647(3) α. The two η⁵-C₅H₄ rings of both Fe^III and Ru^II are essentially staggered and the dihedral angles between the rings of FcH and RcH moieties are less than 5.8°. Typical ferrocenium-type broad singlet ⁵⁷Fe-Mössbauer lines are observed for both salts (1, 2) at all temperatures.     

Dimethyl- and Diethyltin(IV) Compounds with Perfluorobiphenyl-4-Thiolate and Perfluoronaphthalene-2-Thiolate Anions: The Crystal Structure of (CH3)2Sn(C12F9S)2

Compounds (CH₃)₂Sn(C₁₂F₉S)₂ (I), (CH₃)₂Sn(C₁₀F₇S)₂ (II), and (C₂H₅)₂Sn(C₁₀F₇S)₂ (III) were synthesized. Single crystals of Iwere grown and structurally characterized using X-ray diffraction analysis (1590 reflections, R = 0.0209). The crystals are orthorhombic, a = 40.848(8) Å, b = 6.058(1) Å, c = 11.183(2) Å, V = 2767(1) ų, (calcd.) = 2.024 g/cm³, space group Pbcn, Z = 4. The structure is built from monomeric molecules. The coordination polyhedron of the Sn atom (the SnC₂S₂ core) is a distorted tetrahedron. Compounds I–III are volatile when heated in vacuo. Thermolysis of these compounds results in SnO₂ (in air) or SnS₂ (in argon).     

Study of substituent effects on rotational isomers and monomer–dimer equilibria of the 3-carboxy group in 4-substituted (R)-2-(3,4-methylenedioxyphenyl)-6-isopropyloxy-2H-chromen-3-carboxylic acids in dilute CCl4 and CHCl3 solutions by FTIR spectroscopy

FTIR spectra of the title carboxylic acids (I–III) with 4-substituents (H, CH₃ or C₆H₅) and their related compounds IV–VI with 4-(substituted phenyl) groups were measured in dilute CCl₄ and CHCl₃ solutions. The concentration dependence of FTIR spectra of I–IV was also measured in these solutions. These spectra were subjected to curve analysis in order to quantitatively identify the rotational isomers of 3-carboxy group attributable to steric hindrance of the 4-substituents. For I, II and III–VI, two, four and five ν(CO) bands were observed for their carboxy groups, respectively, indicative of monomer–dimer equilibrium and two and three kinds of rotational isomers for II and III–VI, respectively. Compounds III–VI were found to form intra-molecular hydrogen bonds between the trans-type of the 3-carboxy group and the π-electrons in the 4-benzene ring. We have worked out a method to estimate the association constant (K) of complicated monomer–dimer equilibria such as II–VI. The K values of I–IV decrease remarkably in the order of H (I), C₆H₅ (III), CH₃ (II) and C₆H₄-p-OCH₃ (IV) in CCl₄ and I, II, III and IV in CHCl₃; these orders are discussed.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number.     

Fluordiazadiphosphetidine, 20. Mitt. Die Dehydrofluorierung zwitterionischer und die Hydrofluorierung neutraler,hydrazinsubstituierter Fluordiazadiphosphetidine

In the presence ofEt ₃N·PF₅, F₄P^–(CH₃N)₂PF₂NHNH⁺(CH₃)₂ (I) looses one molecule of HF to yield F₃P(CH₃N)₂PF₂NHN(CH₃)₂ (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H⁺⁺(CH₃NPF₄) ₂ ^–– (III) and [CH₃NPF₂NHN(CH₃)₂]₂ (IV). Even in the presence of CsF,II does not react with HF.

     

NMR studies of molecular motion in tetramethylammonium hydroxide pentahydrate

Polycrystalline (CH₃)₄NOH·5 H₂O (I) and (CH₃)₄NOD·5D₂O (II) have been studied by¹H NMR lineshapes, second moments and spin-lattice relaxation times and by²H NMR lineshapes as a function of temperature. From low temperatures the first motion to occur is reorientation of the internally rigid (CH₃)₄N⁺ ion about a uniqueC ₃ axis (E _ta = 8.37 kJ/mol forI,E _a = 9.00 kJ/mole forII), followed closely by pseudo isotropic reorientation of the whole ion (E _a = 18.10 kJ/mol). Motion of the cage molecules (water and hydroxide ion) occurs at higher temperatures with an apparentE _a = 11.30 kJ/mol. There is some evidence of a phase transition inII but notI in the 220–230 K region.²H NMR lineshapes ofII below 220 K indicate static cage molecules. Some of the²H quadrupole coupling constants derived from these spectra correspond to O·O hydrogen-bond distances which are incompatible with the known room temperature structure ofI. Above the possible transition inII the anisotropic²H lineshapes indicate rapid motion of²H among all possible hydrogen-bond sites via transfer along the bonds and molecular reorientation. This motion persists in the high temperature phase but the lineshape becomes isotropic due to the cubic symmetry of this phase. It is possible that¹H or²H tunnelling plays an important part in the motion of the cage molecules and the different phase behaviour ofI andII.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Formation of Cu<Superscript>I</Superscript>(CH<Subscript>3</Subscript>CN)<Subscript>4</Subscript>ClO<Subscript>4</Subscript> in the reactions of copper(II) perchlorate with acetonitrile in the presence of sulfur-containing organic compounds

Cu(ClO₄)₂·6H₂O was shown to react with 2,2′-[propane-1,3-diylbis(thio-2-phenylnemethylidene]-bis(3-pyridylamine) (I) or (5Z)-2-ethoxycarbonylmethyl-(2-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one (II) in the presence of CH₃CN with the reduction of copper(II) to copper(I) and the formation of the tetrahedral complex Cu^I(CH₃CN)₄ClO₄ (III). In the course of the reaction the organic ligands I and II were oxidized to the corresponding sulfoxides.     

Structure of Complexes Formed in the CuX2–Cu–N-Allylisoquinolinium Chloride System (X = Cl,Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C₉H₇N(C₃H₅)]₂Cu^IICl₄ (I), [C₉H₇N(C₃H₅)]Cu^ICl₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^ICl_1.43Br_0.57 · H₂O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P2₁/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) ų, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) ų; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) ų. The structure of I is composed of Cu^IICl₄ ^2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C₉H₇(C₃H₅)]₂Cu₂ ^IX₄ dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.     

Binuclear Pd(II) complexes with chiral ethylenediaminodioxime (H2L) and bis-α-thiooxime (H2L1), the derivative of monoterpenoid(+)-3-carene. Crystal structures of [Pd2(H2L)Cl4] and [Pd2(H2L1)Cl4] · 3CDCl3

Diamagnetic Pd(II) complexes with the chiral ethylenediaminodioxime (H 2 L) and bis-α-thiooxime (H₂L¹), the derivatives of monoterpenoid (+)-3-carene, of the composition Pd₂(H₂L)Cl₄(I), Pd₂(H₂L¹)Cl₄ (II), and the solvate Pd₂(H₂L¹)Cl₄·3DCl₃ (III) were synthesized. The crystal structures of complex I and solvate III were determined from X-ray diffraction data. The structures consist of acentric binuclear molecules with the coordination cores PdN₂Cl₂ (in I) and PdNSCl₂ (in III) in the form of the distorted squares. In complex I, each Pd atom coordinates two N atoms of the tetradentate bridge-cyclic ligand H₂L and two Cl atoms; in compound III, one N and one S atom of the tetradentate bridge-cyclic ligand H₂L¹, and 2 Cl atoms. The CDCl₃ molecules in compound III lie in the cavities formed by the molecules of complex II. In both structures, the PdCl₂ fragments are in the trans-positions. The ¹H NMR spectra indicate that the structures of complexes I, II in solutions are similar to the structures of compounds I, III in the solid state. Original Russian Text ? T.E. Kokina, L.I. Myachina, L.A. Glinskaya, A.V. Tkachev, R.F. Klevtsova, L.A. Sheludyakova, S.N. Bizyaev, A.M. Agafontsev, N.B. Gorshkov, S.V. Larionov, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 2, pp. 120–132.     

Gold(III)pentafluorophenylarylazoimidazole: Synthesis and spectral (H, C, COSY, HMQC NMR) characterisation

Reaction of [Au^III(C₆F₅)₃(tht)] with RaaiR′ in dichloromethane medium leads to [Au^III(C₆F₅)₃ (RaaiR′)] [RaaiR′=p-R-C₆H₄-N=N-C₃H₂-NN-l-R′, (1-3), R = H (a), Me (b), Cl (c) and R′= Me (1), CH₂CH₃ (2), CH₂Ph (3), tht is tetrahydrothiophen]. The nine new complexes are characterised by ES/MS as well as FAB, IR and multinuclear NMR (¹H,¹³C,¹⁹F) spectroscopic studies. In addition to dimensional NMR studies as¹H,¹H COSY and¹H¹³C HMQC permit complete assignment of the complexes in the solution phase.     

Synthesis and molecular structures of lanthanocene amide complexes and their catalytic activity for addition of amines to nitriles

Reaction of (CH₃C₅H₄)₂LnCl(THF) with NaNHAr in a 1:1 molar ratio in THF afforded the amide complexes (CH₃C₅H₄)₂LnNHAr(THF) [(Ar = 2,6-Me₂C₆H_3, Ln = Yb (I), Y (III); Ar = 2,6-ⁱPr₂C₆H₃, Ln = Yb (II)]. X-ray crystal structure determination revealed that complexes I-III are isostructural. The central metal in each complex coordinated to two methylcyclopentadienyl groups, one amide group and one oxygen atom from THF to form a distorted tetrahedron. Complexes I-III and a known complex (CH₃C₅H₄)₂YbNⁱPr₂(THF) IV all can serve as the catalysts for addition of amines to nitriles to monosubstituted N-arylamidines. The activity depended on the central metals and amide groups, and the active sequence follows the trend IV ≈ III < I < II.     

Coordination compounds of cobalt(II), nickel(II), and copper(II) with 4-(3-hydroxyphenyl)-1,2,4-triazole: Synthesis and study

New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co₃L₆(H₂O)₅(C₂H₅OH)](NO₃)₆ · 2H₂O · C₂H₅OH (I), [Ni₃L₆(H₂O)₆](NO₃)₆ · 2H₂O (II), and [M₃L₆(H₂O)₆](ClO₄)₆ · nH₂O (M = Co2⁺, n = 2 (III); Ni²⁺, n = 2 (IV); Cu²⁺, n = 0 (V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy, and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound I, [Co₃L₆(H₂O)₆](ClO₄)₆ · 8C₂H₅OH (IIIa), and [Ni₃L₆(H₂O)₆](ClO₄)₆ · 8C₂H₅OH (IVa) are determined.     

High-temperature spin transition in the iron(II) trifluoromethylsulfonate,perrhenate, and tetraphenylborate complexes with tris(pyrazol-1-yl)methane

New coordination compounds of iron(II) trifluoromethylsulfonate, perrhenate, and tetraphenylborate with tris(pyrazol-1-yl)methane (HC(Pz)₃) of the composition [Fe(HC(Pz)₃)₂]A₂ (A = CF₃SO₃ ⁻ (I), ReO₄ ⁻ (II), and B(C₆H₅)₄ ⁻ (III)) were synthesized and studied by the method of static magnetic susceptibility and IR and electronic spectroscopies. The crystal and molecular structures of compounds I and II were determined by X-ray diffraction analysis. The magnetochemical study of complexes I—III in the interval from 275 to 500 K showed that they possessed the high-temperature spin transition ¹ A ₁ ⇄ ⁵ T ₂ accompanied by thermochromism.     

Structure and properties of double complex salts [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]2[Cu(C2O4)2]3

Double complex salts (DCSs) [Co(NH₃)₆][Fe(CN)₆] (I) and [Co(NH₃)₆]₂[Cu(C₂O₄)₂]₃ (II) and complex [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O (III) are synthesized and investigated by single crystal XRD, crystal optics, and elemental analysis. The crystalline phases of I, II, and III (R-3, P2₁/c, and Pnnm space groups respectively) have the following crystallographic characteristics: a = 10.9804(2) ?, b = 10.9804(2) ?, c = 10.8224(3) ?, V = 1130.03(4) ?³, Z = 3, d _x = 1.65 g/cm³ (I); a = 9.6370(2) ?, b = 10.2452(2) ?, c = 13.2108(3) ?, V = 1932.90(9) ?³, Z = 2, d _x= 1.97 g/cm³ (II), and a = 11.7658(3) ?, b = 11.7254(3) ?, c = 14.1913(4) ?, V = 1304.34(5) ?³, Z = 2, d _x = 1.68 g/cm³ (III). This paper investigates the products of DCS thermolysis in a hydrogen atmosphere: the intermetallic compound CoFe with the bcc parameter a = 2.852 ? for I and a heterogeneous mixture of Co and Cu in the decomposition of II. The coordinated CN⁻ and C₂O₄²⁻ groups then turn into NH₃, hydrocarbons, and CO₂. The dominant hydrocarbon is methane.     

Syntheses, structural determination and binding studies of nine-coordinate mononuclear (EnH2)1.5 [ErIII(Ttha)] · 3H2O and (EnH2)[ErIII(Egta)(H2O)]2 · 6H2O

In this work, the title complexes, (EnH₂)_1.5[Er^III(Ttha)] · 3H₂O (I) and (EnH₂)[Er^III(Egta)(H₂O)]₂ · 6H₂O (II), where En = ethylenediamine, H₆Ttha = triethylenetetramine-N,N,N′,N″,N″’,N″′-hexaacetic acid, H₄Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized. Their structures have been characterized by IR spectroscopy and single-crystal X-ray diffraction techniques. The X-ray diffraction reveals that I is nine-coordinated and crystallizes in the monoclinic crystal space group P2/n with cell dimensions a = 17.6058(16), b = 9.6249(9), c = 20.560(2) ?, β = 109.7440(10)°, and V = 3279.1(5) ?³. Compound II is also nine-coordinated and crystallizes in the monoclinic crystal space group P2₁/n with the cell dimensions a = 12.938(6), b = 12.651(5), c = 14.943(6) ?, β = 105.441(5)°, and V = 2357.5(17) ?³. In I, each EnH₂²⁺ cation connects three adjacent [Er^III(Egta)(H₂O)]⁻ complex anions through hydrogen bonds, while in I, there are two types of EnH₂ ²⁺ anions. One is highly symmetrical, forming hydrogen bonds with two neighboring [Er^III(Ttha)]³⁻ complex anions. The other anion connects three adjacent [Er^III(Ttha)]³⁻ complex anions through hydrogen bonds. These hydrogen bonds lead to the formation of 2D ladder-like layer structure.     

Synthesis and properties of Cu(II) and Pd(ii) complexes with chiral bis-α-sulfanyl oxymes,the derivatives of natural monoterpene, α-pinene

Coordination compounds Cu₂(H₂L¹)Cl₄ (I), Pd₂(H₂L¹)Cl₄ (II), Cu₂(H₂L²)Cl₄ (III), and Pd₂(H₂L²) Cl₄ (IV) with chiral bis-α-sulfanyloximes, the derivatives of the monoterpenoid (−)-α-pinene, were obtained. The complexes I and III are paramagnetic (μ_eff = 2.45 and 2.67 μ_B, respectively), II and IV are diamagnetic. According to IR spectroscopy, in the compounds I–IV the nearest environment of Cu and Pd atoms includes N, S, and Cl atoms. The values of μ_eff and parameters of ESR spectra of the solid phase and solutions of I and III show a binuclear structure of the Cu(II) complexes. Parameters of the ¹H and ¹³C NMR spectra of compounds II and IV indicate the formation of binuclear Pd(II) complexes of C ₂ symmetry and the closure of fivemembered chelate rings PdNSC₂. The PdCl₂ fragments are in transoid position. H₂L¹ and H₂L² are tetradentate bridging chelating ligands.