Synthesis and characterization of complexes of the type [Pt(amine)4]I2 and trans-[Pt(CH3NH2)2(H3CNC(CH3)2)2]I2 by crystallography and multinuclear magnetic resonance spectroscopy

Complexes of the type [Pt(amine)₄]I₂ were synthesized and characterized mainly by multinuclear (¹⁹⁵Pt, ¹H and ¹³C) magnetic resonance spectroscopy. The compounds were prepared with different primary amines, but not with bulky amines, due to steric hindrance. In ¹⁹⁵Pt NMR, the signals were observed between −2715 and −2769 ppm in D₂O. The coupling constant ³J(¹⁹⁵Pt-¹H) for the MeNH₂ complex is 42 Hz. In ¹³C NMR, the average values of the coupling constants ²J(¹⁹⁵Pt-¹³C) and ³J(¹⁹⁵Pt-¹³C) are 18 and 30 Hz, respectively. The crystal structure of [Pt(EtNH₂)₄]I₂ was determined by X-ray diffraction methods. The Pt atom is located on an inversion center. The structure is stabilized by H-bonding between the amines and the iodide ions. The compound with n-BuNH₂ was found by crystallographic methods to be [Pt(n-BuNH₂)₄]₂I₃(n-BuNHCOO). The crystal contains two independent [Pt(CH₃NH₂)₄]²⁺ cations, three iodide ions and a carbamate ion formed from the reaction of butylamine with CO₂ from the air. When the compound [Pt(CH₃NH₂)₄]I₂ was dissolved in acetone, crystals identified as trans-[Pt(CH₃NH₂)₂(H₃CNC(CH₃)₂)₂]I₂ were isolated and characterized by crystallographic methods. Two trans bonded MeNH₂ ligands had reacted with acetone to produce the two N-bonded Schiff base Pt(II) compound.     

Spectroscopic and magnetic properties of diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand with perchlorate transition metal salts. Crystal structure of [Cu(4-pmOpe)2(ClO4)2]

The perchlorate M(II) (M = Cu, Ni, Co) complexes with the diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand of the composition [M(4-pmOpe)₂ (H₂O)₂](ClO₄)₂ (M = Ni, Co) and [Cu(4-pmOpe)₂(ClO₄)₂] were prepared and studied. The ligand contains two donor atoms, i.e. pyridine nitrogen and phosphoryl oxygen atoms. In particular, the crystal structure of [Cu(4-pmOpe)₂(ClO₄)₂] was determined by the X-ray method. Its structure consists of a one-dimensional polymeric chain in which copper(II) ions are N,O-bridged by two 4-pmOpe organic ligands in a trans arrangement. Two perchlorate ions occupy the fifth and the sixth coordination sites. The Cu?Cu distance is 9.180 Å. The crystal packing is determined by the weak intermolecular C-H?O hydrogen contacts. The coordination compounds were identified and characterized by elemental analysis, spectroscopic and magnetic studies. Spectroscopic and magnetic results of the copper(II) compound are presented in the light of the crystal structure. The magnetic data indicate very weak intra- and interchain magnetic exchange interactions (J^’ = −0.43 and zJ^’ = 0.29 cm⁻¹, respectively). The spectroscopic and magnetic properties of the Co(II) and Ni(II) complexes indicate octahedral and polymeric structure of both compounds in which 4-pmOpe ligand also acts as N,O-bridge between metal ions.     

Low-dimensional compounds containing cyano groups. XIX. Crystal structure, spectroscopic, thermal and magnetic properties of {[Cu(tn)2]3[Pt(CN)4]2}[Pt(CN)4] (tn = 1,3-diaminopropane) complex

Violet prismatic crystals of {[Cu(tn)₂]₃[Pt(CN)₄]₂}[Pt(CN)₄] (tn = 1,3-diaminopropane) were crystallized from the water-methanol solution containing CuCl₂·2H₂O, tn and K₂[Pt(CN)₄]·3H₂O. Prepared complex was characterized using elemental analysis, infrared and UV-Vis spectroscopy, magnetic measurement and thermal analysis. X-ray analysis revealed an ionic character of the complex containing mononuclear square planar [Pt(CN)₄]²⁻ complex anions and penta-nuclear [Cu(tn)₂-Pt(CN)₄-Cu(tn)₂-Pt(CN)₄-Cu(tn)₂]²⁺ complex cations. The inner Cu(II) atom of the complex cation is hexa-coordinated, whereas two crystallographically equivalent peripheral Cu(II) atoms are penta-coordinated in the shape of a deformed square pyramid. Four v(CN) absorption bands observed in the IR spectrum are in agreement with the higher number of crystallographically different cyano groups and a broad highly asymmetric band observed in the reflectance UV-Vis spectrum is consistent with the presence of both hexa- and penta-coordinated Cu(II) atoms in the structure. The temperature dependence of the inverse susceptibility suggests the presence of a weak antiferromagnetic exchange coupling between Cu(II) ions. The complex is stable up to 210 °C when its two-stage thermal decomposition starts.     

Structure and reactivity of [Ru(2,3-Medpp)2Cl2]

The structure and reactivity of the complex [Ru(2,3-Medpp)₂Cl₂](PF₆)₂ (2,3-Medpp⁺=2-[2-(1-methylpyridiniumyl)]-3-(2-pyridyl)pyrazine) was investigated by X-ray diffraction (XRD), ¹H NMR, redox, and UV-Vis absorption measurements. X-ray analysis shows that crystals obtained from an acetonitrile-toluene solution contain the trans-Cl₂, trans-pyrazine isomeric form, while ¹H NMR and redox measurements on the main product of the synthetic workup indicate the presence of the trans-Cl₂, cis-pyrazine isomer. In the dark at 70 °C, the complex [Ru(2,3-Medpp)₂Cl₂]²⁺ reacts slowly in acetonitrile isomerizing to the cis-[Ru(2,3-Medpp)₂(CH₃CN)Cl]³⁺ species. Under ambient light in the presence of excess AgNO₃ the cis-[Ru(2,3-Medpp)₂(CH₃CN)₂]⁴⁺ species is obtained.     

Electronic effects on the interactions of complexes [Ru(phen)2(p-L)] (L=MOPIP, HPIP, and NPIP) with DNA

In order to explore the electronic effects of Ru(II) complexes binding to DNA, a series of Ru(II) complexes [Ru(phen)₂ (p-MOPIP)]²⁺ (1), [Ru(phen)₂ (p-HPIP)]²⁺ (2), and [Ru(phen)₂(p-NPIP)]²⁺ (3) were synthesized and characterized by elementary, ¹H NMR, and ES-MS analysis. The binding properties of these complexes to CT-DNA were investigated with spectroscopic methods and viscosity experiments. Furthermore, the computations for these complexes applying the density functional theory (DFT) method have also been performed. The results show that all of these complexes can well bind to DNA in intercalation mode and DNA-binding affinity of these complexes is greatly influenced by electronic effects of intercalating ligands. The intrinsic binding constants for 1, 2, and 3 are 0.20, 0.69, and 1.56 × 10⁵ M⁻¹, respectively. This order is in accordance with that of the electron-withdrawing ability of substituent [-OR < -OH < -NO₂]. Such a trend in electronic effects of Ru(II) complexes binding to DNA can be reasonably explained by the DFT calculations.     

Hydroxylation of a methyl group: synthesis of [Cu2(btmmO)2I] and of [Cu2(btmmO)2] containing the novel ligand {bis(trimethylmethoxy)guanidino}propane (btmmO) by copper-assisted oxygen activation

The reaction of the bisguanidine copper(I) compounds [Cu(btmgp)I] and [Cu₂(btmgp)₂][PF₆]₂ with molecular oxygen afforded at low temperatures complexes containing the bis-μ-oxo dicopper(III) core, which is capable to hydroxylate one of the N-CH₃-groups of the {bis(tetramethyl)guanidino}propane ligands. The formation of the novel ligand {bis(trimethylmethoxy)guanidino}propane (btmmO) is reported as it represents the first hydroxylation of a N-methyl group. The products of this reaction are novel alkoxo-bridged binuclear copper complexes, namely [Cu₂(btmmO)₂I]⁺ containing an iodide ion in a novel bridging situation, as well as [Cu₂(btmmO)₂]²⁺ which have been identified in their complex salts and [Cu₂(btmmO)₂][PF₆]₂ · 2MeCN, respectively. Concomitantly, the hydroxo-bridged binuclear copper compounds [Cu₂(btmgp)₂(μ-OH)₂]I₂ and [Cu₂(btmgp)₂(μ-OH)₂][PF₆]₂ are formed as couple products. The formation of the bis-μ-oxodicopper(III) complexes was monitored by UV/Vis-spectroscopy, and the reaction products were characterised by X-ray diffraction, vibrational spectroscopy and elemental analysis.     

Crystal structure, magnetic properties and Mössbauer studies of [Fe(qsal)2][Ni(dmit)2]

A new compound of formula [Fe(qsal)₂][Ni(dmit)₂] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit²⁻ = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)₂]-based complexes, and more particularly [Fe(qsal)₂][Ni(dmit)₂] · 2CH₃CN.     

Preparation, crystal structures and spectroscopic properties of novel [MCl3 − n(P)3 + n] (M = Co, Rh; n = 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane

Cobalt(III) and rhodium(III) complexes of the series of [M^IIICl_3 − n(P)_3 + n]ⁿ⁺ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl₃(tdmme)] < [MCl₂(tdmme)(PMe₃)]⁺ < [MCl(tdmme)(dmpe)]²⁺ (dmpe = 1,2-bis(dimethylphosphino)ethane) < [M(tdmme)₂]³⁺ for both Co^III and Rh^III series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)₂]³⁺). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]²⁺ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF₄)₂ showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 Å than those in the dmpe complex. Furthermore, the first d-d transition energy of the Co^III complexes and the ¹J_Rh-P(tdmme) coupling constants observed for the Rh^III complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.     

Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2]

The reaction of with Co(dmgBF₂)₂(H₂O)₂ in 1.0 M HClO₄/LiClO₄ was found to be first-order in both reactants and the [H⁺] dependence of the second-order rate constant is given by k_2obs = b/[H⁺], b at 25 °C is 9.23 ± 0.14 × 10² s⁻¹. The [H⁺] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for as K_a = 9.5 × 10⁻³ M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH₂)₅OH^2+/+ were used to estimate an electron self-exchange rate constant of k₂₂ = 1.7 × 10⁻⁴ M⁻¹ s⁻¹ for .     

[S2], [S3], and [N3] coordination modes of hydrotris(thioxotriazolyl)borato. Zinc, nickel, cobalt, and bismuth complexes

The ligand hydrotris(1,4-dihydro-3-methyl-4-phenyl-5-thioxo-1,2,4-triazolyl)borato (Tr^Ph,Me) was synthetized as natrium salt and the complexes [Zn(Tr^Ph,Me)₂] · 7.5H₂O · 1.5CH₃CN (2a), [Zn(Tr^Ph,Me)₂] · 8DMF (2b), [Co(Tr^Ph,Me)₂] · 8DMF (3a), [Ni(Tr^Ph,Me)₂] · H₂O · 6DMSO (4a), [Bi(Tr^Ph,Me)₂]NO₃ (5), have been isolated and structurally characterized by X-ray diffraction. In the zinc derivatives the ligand adopts different denticity and coordination modes, η² and [S₂] for 2a and η³ and [N₃] for 2b, depending on the crystallization solvent, giving rise to tetrahedral and octahedral geometry, respectively. In the octahedral cobalt and nickel complexes the ligand is η³ and [N₃] coordinated whereas in the bismuth complex the η³ and [S₃] coordination is exhibited.     

O-Alkylthio- and O-alkylselenooxalate iron complexes: Structures of CpFe(CO)2ECOCO2Me and [CpFe(CO)2ECO]2

When the iron sulfide complexes (μ-S_x)[CpFe(CO)₂]₂ (x = 2, 3) are treated with O-alkyl oxalyl chlorides ROCOCOCl the complexes CpFe(CO)₂SCOCO₂R (1) [R = Me (a), Et (b)] are obtained. Similarly, the complexes CpFe(CO)₂SeCOCO₂R (2) are obtained from the analogous iron selenide (μ-Se)[CpFe(CO)₂]₂ reaction with the same reagents. Treatment of the iron selenide with half equivalent of oxalyl chloride produces the dimeric complex [CpFe(CO)₂SeCO]₂ (3). The new complexes, 1, 2 and 3, have been characterized by elemental analyses, IR and ¹H NMR spectroscopy. The solid state structures of 1a, 2a, 3 and [CpFe(CO)₂SCO]₂ (4) were determined by an X-ray crystal structure analysis.     

Synthesis, characterisation and substitution kinetics of unusually labile trans-[Co(tmen)(diamine)Cl2] complexes

The mixed diamine complexes trans-[Co(tmen)(diamine)Cl₂]⁺ have been synthesised (tmen = NH₂C(Me)₂C(Me)₂NH₂; diamine = en = NH₂(CH₂)₂NH₂, and ibn = NH₂C(Me)₂CH₂NH₂). Replacement of one en ligand in trans-[Co(en)₂Cl₂]⁺ by one tmen ligand engenders an enormous rate enhancement (2000-fold) for acid hydrolysis. Solvolysis rates have been measured in Me₂SO and DMF for these complexes and also trans-[Co(tmen)₂Cl₂]⁺ which is more reactive again (10⁴-fold). The measured reactivities in DMF at 2 °C establish that the kinetic effect of replacing each en by tmen is incremental, and the extreme base catalysed racemisation rate for (+)-[Co(tmen)₃]³⁺ can now be explained on this basis.     

A new mixed-valence hexanuclear cobalt complex, [Co4Co2(dea)2(Hdea)4)(piv)4](ClO4)2·H2O: Synthesis, crystal structure and magnetic properties

A new Co^II/Co^III hexanuclear complex, [Co₄^IICo₂^III(dea)₂(Hdea)₄)(piv)₄](ClO₄)₂·H₂O 1, has been obtained by reacting cobalt(II) perchlorate, diethanolamine, and pivalic acid (H₂dea = diethanolamine and piv = pivalato anion). The cobalt ions are held together by four μ₃ and four μ₂ alkoxo bridges as well as by four syn-syn carboxylato groups. The hexanuclear motif contains four Co(II) and two Co(III) ions. The {Co^II₄Co^III₂(μ₂-O)₄(μ₃-O)₄} core can be described as a four face-sharing monovacant and bivacant distorted heterocubane units. The cobalt(III) ions are hexacoordinated. Two of the cobalt(II) are hexacoordinated, while the two others are pentacoordinated with a bipyramidal stereochemistry. The magnetic properties of 1 have been investigated in the temperature range 1.9-300 K. Compound 1 exhibits an overall antiferromagnetic behaviour with a ground singlet spin state.     

Synthesis and characterization of two novel cobalt (II) phosphine complexes: crystal structures of [CoCl3(Cy2PCH2PCy2H)] and [Co(NO3)2(Cy2PCH2PCy2O)]. Cy = cyclohexyl, C6H11

The complexes [(Cy₂PCH₂PCy₂H)CoCl₃] (1) and [(Cy₂PCH₂PCy₂O)Co(NO₃)₂] (2), Cy = cyclohexyl (C₆H₁₁), have been prepared and characterized by EPR, UV-Vis, microanalysis and X-ray crystallography. The reaction CoCl₂ · 6H₂O and dcpm, dcpm = bis(dicyclohexylphosphino)methane, was found to form the monomeric, four coordinate, thermochromic and paramagnetic complex [(Cy₂PCH₂PCy₂H)CoCl₃] (1). Of particular interest is the formation of a zwitterion, or inner salt, in which the dangling phosphine adds a hydrogen atom, giving the phosphorus a +1 formal charge. The molecule adopts a pseudo-tetrahedral geometry around the central cobalt atom to which the cyclohexyl groups bind in an equatorial fashion to the phosphine. The reaction of Co(NO₃)₂ · 6H₂O and dcpm in a toluene/methanol/methylene chloride mixture yields the pseudo-octahedral complex [(Cy₂PCH₂PCy₂O)Co(NO₃)₂] (2). The cobalt is in the +2 oxidation state with one of the phosphorus atoms again having a +1 formal charge. The complex adopts a pseudo-octahedral geometry around the central cobalt atom with the cyclohexyl groups binding in an equatorial fashion to the phosphine similar to [(Cy₂PCH₂PCy₂H)CoCl₃].     

Synthesis, characterization, electrochemical and spectroscopic investigation of cobalt(III) Schiff base complexes with axial amine ligands: The layered crystal structure of [Co(salophen)(4-picoline)2]ClO4 · CH2Cl2

Cobalt(III) complexes with potentially tetradentate salophen (H₂salophen = N,N′-bis(salicylidene)-1,2-phenylenediamine) as equatorial ligand and with different axial amine ligands (NH₃, cyclohexylamine, aniline, 4-picoline and pyridine) were synthesized and characterized by IR, ¹H NMR, elemental analysis. Electronic spectra and electrochemical properties of the complexes were studied in DMF solutions. The lowest energy transitions, which occur between 464.8 and 477 nm, are attributed mainly to the intraligand charge transfer, confirmed by Zindo/S electronic structure calculations. The reduction potentials of Co(III)/Co(II) are more affected than those of Co(II)/Co(I) by the axial amine ligands. The crystal structure of the [Co^III(salophen)(4- picoline)₂]ClO₄ · CH₂Cl₂ was determined, indicating that the cobalt(III) center is six coordinated surrounded by the tetradentate salophen ligand and two 4-picoline ligands. The crystal packing of the complex shows a layered structure, in which the perchlorate counter ions and also the lattice solvent molecules are intercalated between the bc planes of the complex cations.     

New metal complexes of N2S2 tetradentate ligands: Synthesis and spectral studies

New tetradentate ligands 2-(2-mercaptoethylthio)-N-(pyridin-2-ylmethyl)acetamide H₂L¹ and 2-chloro-2-(2-mercaptoethylthio)-N-(pyridin-2-ylmethyl)acetamide H₂L² were synthesised from the reaction of 2-aminomethanepyridine with 1,4-dithian-2-one and 3-chloro-1,4-dithian-2-one, respectively. Monomeric complexes of these ligands, of general formulae K[Cr^III(Lⁿ)Cl₂], K₂[Mn^II(Lⁿ)Cl₂] and [M(Lⁿ)] (M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) or Hg(II); n = 1, 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content and conductance. These studies revealed octahedral geometries for the Cr(III), Mn(II) complexes, square planar for Ni(II) and Cu(II) complexes and tetrahedral for the Fe(II), Co(II), Zn(II), Cd(II) and Hg(II) complexes. The study of complex formation via molar ratio in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M:L) as (1:1).     

Rb2[B12(OH)12]·2H2O and Rb2[B12(OH)12]·2H2O2: Hydrate and perhydrolate of rubidium dodecahydroxo-closo-dodecaborate

The orthorhombically crystallizing salts Rb₂[B₁₂(OH)₁₂]·2H₂O (a = 1576.81(9), b = 813.08(5), c = 1245.32(7) pm) and Rb₂[B₁₂(OH)₁₂]·2H₂O₂ (a = 1616.54(9), b = 814.29(5), c = 1260.12(7) pm) could be prepared from Rb₂[B₁₂H₁₂] and hydrogen peroxide. Both crystal structures were determined by X-ray single crystal diffraction and refined in the space group Cmce. They are not isostructural to the other compounds containing icosahedral dodecahydroxo-closo-dodecaborate dianions [B₁₂(OH)₁₂]²⁻ and potassium, rubidium or cesium cations already known to literature, but both title compounds crystallize quasi-isotypically exhibiting Rb⁺ cations in 10-fold oxygen coordination. The hydrogen peroxide adduct (Rb₂[B₁₂(OH)₁₂]·2H₂O₂) is explosive on shock and heat, while the hydrate (Rb₂[B₁₂(OH)₁₂]·2H₂O) is not.     

Structural characterization, electrochemistry, and spectroelectrochemistry of trans-dioxorhenium(V) complex with 4-methoxypyridine, [ReO2(4-MeOpy)4]PF6, and characterization of [ReO2(4-MeOpy)4] generated electrochemically

Crystal structure of [ReO₂(4-MeOpy)₄][PF₆] (4-MeOpy = 4-methoxypyridine) complex has been examined by the single crystal X-ray analytical method. This complex shows a trans-dioxo geometry (average Re-O bond length = 1.766(2) Å) and its equatorial plane is occupied by four 4-MeOpy molecules (average Re-N bond length = 2.156(4) Å). Electrochemical reaction of [ReO₂(4-MeOpy)₄]⁺ in CH₃CN solution containing tetra-n-butylammonium perchlorate as a supporting electrolyte has been studied using cyclic voltammetry at 24 °C. Cyclic voltammograms show one redox couple around 0.65 V (E_pa) and 0.58 V (E_pc) [versus ferrocene/ferrocenium ion redox couple, (Fc/Fc⁺)]. Potential differences between two peaks (ΔE_p) at scan rates in the range from 0.01 to 0.10 V s⁻¹ are 65 mV, which is almost consistent with the theoretical ΔE_p value (59 mV) for the reversible one electron transfer reaction at 24 °C. The ratio of anodic peak currents to cathodic ones is 1.04 ± 0.03 and the (E_pa + E_pc)/2 value is constant, 0.613 ± 0.001 V versus Fc/Fc⁺, regardless of the scan rate. Spectroelectrochemical experiments have also been carried out by applying potentials from 0.40 to 0.77 V versus Fc/Fc⁺ with an optically transparent thin layer electrode. It was found that the UV-visible absorption spectra show clear isosbestic points at 228, 276, and 384 nm, and that the electron stoichiometry is evaluated as 1.03 from the Nernstian plot. These results indicate that the [ReO₂(4-MeOpy)₄]⁺ complex is oxidized reversibly to the [ReO₂(4-MeOpy)₄]²⁺ complex. Furthermore, it was clarified that the [ReO₂(4-MeOpy)₄]²⁺ in CH₃CN has the characteristic absorption bands at 236, 278, 330, 478, and 543 nm and their molar absorption coefficients are 4.3 × 10⁴, 4.5 × 10³, 1.0 × 10⁴, and 6.1 × 10³ M⁻¹ cm⁻¹ (M = mol dm⁻³), respectively.     

Functionalised dithiocarbamate complexes: Synthesis and molecular structures of bis(2-methoxyethyl)dithiocarbamate complexes [M{S2CN(CH2CH2OMe)2}2] (M = Ni, Cu, Zn) and [Cu{S2CN(CH2CH2OMe)2}2][ClO4]

The bis(2-methoxyethyl)dithiocarbamate complexes [M{S₂CN(CH₂CH₂OMe)₂}₂] (M = Ni, Cu, Zn, Pd) are readily prepared and the three lighter complexes have been crystallographically characterised. Disproportionation of [Cu{S₂CN(CH₂CH₂OMe)₂}₂] upon addition of Cu(ClO₄)₂ · 6H₂O affords the copper(III) complex [Cu{S₂CN(CH₂CH₂OMe)₂}₂][ClO₄] which has also been crystallographically characterised. Unlike other copper(III) dithiocarbamate salts, there are no intermolecular cation-cation or cation-anion interactions.     

Vibrational and structural mapping of [Os(bpy)3] and [Os(phen)3]

Structural changes between [Os^IIL₃]²⁺ and [Os^IIIL₃]³⁺ (L: 2,2′-bipyridine; 1,10-phenanthroline) and molecular and electronic structures of the Os^III complexes [Os^III(bpy)₃]³⁺ and [Os^III(phen)₃]³⁺ are discussed in this paper. Mid-infrared spectra in the ν(bpy) and ν(phen) ring stretching region for [Os^II(bpy)₃](PF₆)₂, [Os^III(bpy)₃](PF₆)₃, [Os^II(phen)₃](PF₆)₂, and [Os^III(phen)₃](PF₆)₃ are compared, as are X-ray crystal structures. Absorption spectra in the UV region for [Os^III(bpy)₃](PF₆)₃ and [Os^III(phen)₃](PF₆)₃ are dominated by very intense absorptions (ε = 40 000-50 000 M⁻¹ cm⁻¹) due to bpy and phen intra-ligand π → π^∗ transitions. In the visible region, relatively narrow bands with vibronic progressions of ∼1500 cm⁻¹ appear, and have been assigned to bpy or phen-based, spin-orbit coupling enhanced, ¹π → ³π^∗ electronic transitions. Also present in the visible region are ligand-to-metal charge transfer bands (LMCT) arising from π(bpy) → t_2g(Os^III) or π(phen) → t_2g(Os^III) transitions. In the near infrared, two broad absorption features appear for oxidized forms [Os^III(bpy)₃](PF₆)₃ and [Os^III(phen)₃](PF₆)₃ arising from dπ-dπ interconfigurational bands characteristic of dπ⁵Os^III. They are observed at 4580 and 5090 cm⁻¹ for [Os^III(bpy)₃](PF₆)₃ and at 4400 and 4990 cm⁻¹ for [Os^III(phen)₃](PF₆)₃. The bpy and phen infrared vibrational bands shift to higher energy upon oxidation of Os(II) to Os(III). In the cation structure in [Os^III(bpy)₃](PF₆)₃, the Os^III atom resides at a distorted octahedral site, as judged by ∠N-Os-N, which varies from 78.78(22)° to 96.61(22)°. Os-N bond lengths are also in general longer for [Os^III(bpy)₃](PF₆)₃ compared to [Os^II(bpy)₃](PF₆)₂ (0.010 Å), and for [Os^III(phen)₃](PF₆)₃ compared to [Os^II(phen)₃](PF₆)₂ (0.014 Å). Structural changes in the ligands between oxidation states are discussed as originating from a combination of dπ(Os^II) → π^∗ (bpy or phen) backbonding and charge redistribution on the ligands as calculated by natural population analysis.