The Vibrational Spectra of Complexes with Planar Monothiooxamides. III. The Palladium(II) Complexes of Neutral Monothiooxamides

The new complexes trans-[PdX₂(H₄MTO)2] (X = Cl, Br, I), trans-[PdX₂(H₃MMTO)2] (X = Cl, Br, I), trans-[PdX₂(SH₃)2] (X = Cl, Br), [Pd(H₄MTO)₄]CI₂ and [Pd(H₃MMTO)₄]CI₂, where H₄MTO = monothiooxamide, H₃MMTO = N(o)-methylmonothiooxamide and SH₃ = N(s)-methylmonothiooxamide, have been prepared. The complexes were characterized by elemental analyses, conductivity measurements, X-ray powder patterns, thermal methods and spectroscopic (UV/VIS, FT-IR, Laser-Raman) studies. The vibrational analysis of the complexes is given using NH/ND and CH₃/CD₃ isotopic substitutions. Monomeric square planar structures are assigned for the complexes in the solid state. The neutral monothiooxamides behave as monodentate ligands coordinating through their thioamide sulfur atom. The complex [Pd(SH2)2] was isolated during the thermal decomposition of trans-[PdCl₂(SH₃)₂].     

Vibrational Spectra and Normal Coordinate Analysis of Diamminediiodidezinc(II) with 15N and 2H Isotopic Substitution.

The Raman and IR. spectra of solid diamminediiodidezinc (II) with ¹⁵N and ²H isotopic substitution have been measured. The spectra have been interpreted assuming C_2v symmetry for the Zn(NH₃)₂I₂ complex structure. The skeletal stretching metal-ligand modes v_s(ZnN), v_as(ZnN), v_s(ZnI), v_as(ZnI) as well as the three bending modes δ(NZnN), δ(IZnI) and δ(IZnN) were assigned by comparison with the spectra of Zn(NH₃)₂C1₂ and Zn(NH₃)₂Br₂, and by the observed isotopic shifts of the frequencies. A normal coordinate analysis for the whole complex was carried out using the Local Symmetry Force Field Model.     

Laser Raman Spectra of Crystalline Chloromercurate(II) Complexes

Abstract

The laser Raman spectra of crystalline [(CH₃)₄N] HgCl₃ and [(CH₃)₄N]₂HgCl₄ have been studied in the 400–20 cm^?1 region. All expected Raman active modes for the HgCl₃ ^? and HgCl₄ ^?2 ions are observed and assignments of the vibrational frequencies are made in relation to the structure of the anions.     

Vibrational spectra of lead(II) oxalate

The infrared and Raman spectra of anhydrous lead oxalate (PbC₂O₄) were recorded and discussed on the basis of its structural peculiarities. Some comparisons with other previously investigated metallic oxalates were made. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational Behavior of Transition Metal Cupferronato Complexes: Raman Studies on Cobalt(II) Cupferronato Derivatives

The FT-Raman spectrum of cupferron, [PhN₂O₂]NH₄ and the micro-Raman spectra of the new corresponding cobalt(II) cupferronato complexes, CoL₂A₂, L = PhN₂O₂, a = H₂O, MeOH, o-C₆H₄(NH₂)₂, p-C₆H₄(NH₂)₂ and CoL₂A, a = (-C₆H₄NH₂-p)₂ were recorded and discussed. All the complexes show a Raman band at about 1302 cm¹ and the characteristic v(N-N) and δ(ONNO) modes of the anionic ligand. the vibrational analysis of the title compounds reveals the electron delocalisation over the N-nitroso-N-hydroxylaminato (ONNO) unit, as well as the bidentate coordination of the cupferronato ligand to the metal center through the oxygen atoms.     

The Synthesis,Vibrational Spectra,Electronic Spectra,and Thermal Analysis of Some Mixed Complexes with Planar Dithiooxamides

Planar Pd(LH)₂ complexes (LH₂ = H₂N C S C S N H₂, CH₃HNCSCSNHCH₃) form mixed polymeric complexes with Ni(II), Cu(II), Zn(II) and Cd(II) in alcalic media, where the planar Pd(LH)₂ complexes act as tetradentates with N-coordination. The electronic spectra and thermal behaviour are discussed, a thorough investigation of the i.r. spectra is presented and special attention has been given to the H/D, CH₃/CD₃ and ⁵⁸Ni/⁶²Ni, ⁶³Cu/⁶⁵Cu and ⁶⁴Zn/⁶⁸Zn isotopic shifts.     

A Study on the Spectra Characterization of Ruthenium(Ii) Complexes

Abstract

A series of Ru(II) complexes have been synthesized, and their electronic spectra and NMR spectroscopy properties were characterized. the chemical shifts of aromatic protons of [Ru(bpy)₃] (PF₆)₂, [Ru(phen)₃](ClO₄)₂ and [Ru(bqdi)₃](PF₆) move downfield, but the resonance peaks of cis-Ru(bpy)₂Cl₂ shift upfield. Within the visible spectra of the ruthenium(II) complexes appear a relatively high oscillator strength which is referred to as the π(Ru)→? (ligands) transition.     

Vibrational spectroscopic investigation of the hydrates of manganese(II) oxalate

The three known hydrates of manganese(II) oxalate, α‐MnC₂O₄ · 2H₂O, γ‐MnC₂O₄ · 2H₂O and MnC₂O₄ · 3H₂O were synthesized by known procedures and characterized by X‐ray powder diffractometry. Their infrared (IR) and Raman spectra were recorded and discussed on the basis of its structural peculiarities allowing to establish some interesting relations between them and with other, previously investigated, oxalate complexes. The IR spectra of partially deuterated samples of α‐MnC₂O₄ · 2H₂O were also discussed, reinforcing some of the performed assignments. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational Spectroscopic Studies of 3,4-Lutidine Metal (II) Tetracyanonickelate Complexes

Infrared and Raman spectra of seven new metal (II) 3,4-lutidine tetracyanonickelate complexes, M(3,4 L)₂ Ni(CN)₄ [where 3,4 L = 3,4 - dimethyl-pyridine or 3,4-lutidine; M = Mn, Fe, Co, Zn, Ni, Cu or Cd] (abbreviated to M - Ni - 3,4 L) have been investigated. Spectroscopic and magnetic susceptibility measurements indicate that the compounds have the structure of Hofmann-type complexes. The copper complex has spectral features different from the other compounds.     

Infrared Spectra of Morfolonium (mpH)2Mo2Cl6(H20)2(I),(mpH)2Mo2ClxBr6-x(H2O)2(II)/ (mpH)2Mo2Br6(H2O)2(III) and the Pyridinium (PyH)2Mo2I6(H2O)2(IV)Hexahalo-di(aquo): dimolybdate(II) Complexes,Containing Quadruple Metal-Metal Bounds

Abstract

The electronic (800–400 nm), infrared (4000–200,400–20 cm^?1), ordinary Raman (400–200 cm^?1) spectra of morpholinium and the pyridium hexahalo-di(aquo) dimolybdate(II) complexes, containing quadruple metal-metal bonds were investigated. The electronic spectra of the solid compounds at various temperatures (25,100 and 300K) demonstrate intense and structured bands in the visible region (510–582 nm) attributed to the expected δ→δ? transitions.

From the infrared and Raman spectra, the skeletal stretching modes in these complexes have been localized, and the charectenstic bands of these ions were observed in the expected regions.

Finally, the ionic interections were relatively weak, but the existance of phenomena was perceptible and the result was obtained in agreement with X-ray data.     

The Vibrational Spectra of (1-Diacetylmonoximeimino-3-diacetylmonoximatoiminopropane)-methylaquocobalt (III), Perchlorate

Metal complexes of the tetradentate ligand bis(diacetyl-monoximeimino)propane 1,3 = [(DOH)₂pn] are interesting in several respects. They are representatives of molecular systems containing very short hydrogen bonds; moreover, the organo-cobalt derivatives were reported as first examples of stable water-soluble compounds besides Vitamin B₁₂ coenzyme and alkylcobalamines ¹. From this point of view they were extensively investigated as models of Vitamin B₁₂ ². However, vibrational data concerning these complexes are rather scarce: at our knowledge only a limited assignment was proposed by UHLIG and FRIEDRICH³ for some Ni derivatives.     

Infrared and Raman Spectra of Some Iodide-Bridged Complexes of Mercury (II)

The IR and Raman Spectra of pentaiododimercurate (II) and octaiodotrimercurate (II) anionic complexes have been obtained in the solid state and interpreted in terms of halogen-bridged structures. Spectroscopic and chemical evidences support a dimeric structure for the pentaiododimercurate (II) anion.

The addition of HgBr₂ and HgI₂ to tetraiodocadmate (II), mercurate (II) and tetrabromocadmate (II) species have also been studied. The vibrational spectra also support halogen-bridged structures for these new mixed binuclear complexes.     

Fourier Transform Infrared and Raman Spectra of 4-Vinylpyridine and its Transition Metal(II) Tetracyanonickelate Complexes

Abstract

Infrared and Raman spectra (4000-200 cm^?1) were recorded for 4-vinylpyridine and vibrational assignments made for fundamental modes on the basis of frequency shifts of the coordinated ligand, of the group vibrational concept and comparison with the assignments for related molecules. the infrared spectra of M(4-vinylpyridine)₂Ni(CN)₄ (M=Mn, Cd, Fe, Co, Ni or Cu) are reported.     

Vibrational spectra of clioquinol and its Cu(II) complex

The infrared and Raman spectra of 5‐chloro‐7‐iodo‐8‐hydroxyquinoline (clioquinol, CQ) and that of its Cu(II) complex of stoichiometry [Cu(CQ)₂] were recorded and briefly discussed. Some comparisons were made with related complexes. The interest of the investigated systems in relation to Alzheimer's disease is briefly commented. Copyright © 2006 John Wiley & Sons, Ltd.     

An Infrared Spectroscopic Study of Crystalline Copper (II) Propionate and Butyrate

Abstract

Abstract: The vibrational spectra of crystalline anhydrous copper (II) propionate and butyrate were studied by FT-IR spectroscopy. A detailed assignment of the spectra of both compounds is presented and discussed. It is shown that the presence of two non-equivalent sets of carboxylate ligands within the crystals gives rise to several band splittings, which are particularly evident in those bands ascribable to normal modes involving predominantly the -C_βH₃ or -C_βH₂-fragments. In addition, the vibrational assignments made for the studied molecules are shown to be very useful to help understanding the much more complex spectra of long chain copper carboxylates.     

Vibrational spectra of polaprezinc,a polymeric Zn(II) complex of carnosine

Polaprezinc, the Zn(II) complex of the dipeptide carnosine (β‐alanyl histidine) presents an interesting biological and pharmacological activity, specially as an anti‐ulcer agent. The infrared and Raman spectra of this compound were recorded and briefly discussed. Some comparisons were made with related complexes and with free carnosine. The results confirm the coordination environment of the Zn(II) cation, constituted by the terminal amino N‐atom, the deprotonated amide N‐atom and one carboxylate oxygen of one dipeptide molecule and the N‐atom of the imidazole moiety of a second carnosine molecule. Copyright © 2007 John Wiley & Sons, Ltd.     

Vibrational Studies of Palladium(II) Acetate Compounds Ii. Infrared Spectra of the Diethylamine Adduct of Palladium(II) Acetate

Recorded and discussed are the infrared spectra of the diethylamine adduct of palladium(II) acetate. An empirical assignment of the spectra is proposed. The palladium-oxygen bonds in the adduct are not much different in strength from those in hexa-μ-acetato-triangulo-tripalladium(II)-water (2/1). The diethylanine molecules are present as such, as evidenced by the appearance of a rather strong band attributed to the N-H stretching vibrations.     

Spectroscopic Study of the Interaction of Mitoxantrone with Copper(I), Copper(II), and Neocuproine

Both reductive and oxidatlve mode of metabolism have been hypothesized for the antitumor agent mitoxantrone. This work aims to better understand the redox properties of mitoxantrone in the presence of the physiological redox couple, copper(I)/copper(II), by means of polarograpy and spectrophotometry. The first quasi-reversible one-electron reduction of mitoxantrone to the semiquinone and the second reduction to the hydroquinone have been shown to be considerably affected by copper. Visible spectra of mitoxantrone-copper mixtures in nitrogen and oxygen purged solutions taken in a one-week period exhibit varying degrees of complexation and oxido-reduction.

When copper(II), neocuprolne and mitoxantrone are mixed in a certain ratio in pH 7. 4 phosphate buffer solution, two new peaks at 584 and 632 nm emerge in the spectra indicating a ternary charge transfer complex. The complex atoichiometry was established as Cu(IT): neocuproine: tritoxan-trone = 2:4:1 by Job's method of continuous variations. The ternary complex is sensitive to the relative concentrations of mitoxantrone and copper(II), an excess of the latter giving rise to complete red ox products. This complex may be important in modeling the drug's oxidative mode of ant tumor action.     

银(Ⅰ)、镉(Ⅱ)4-巯基吡啶配合物的光谱研究

采用常规溶液反应蒸发法以4-巯基吡啶(简写为4-MPy)为有机配体与银、镉的硝酸盐合成了两种金属有机配合物。并利用红外、拉曼、紫外-可见光谱技术对4-MPy及合成的配位化合物进行了研究,对主要红外和拉曼谱带进行了经验归属,并进一步讨论了配体和配合物的特征吸收谱带与配合物结构间的关系。在红外光谱中,配体在1 459cm-1处的吸收峰归属为CC和CN复合振动峰,形成配合物后在两种配合物中,此吸收峰分别向高波数位移至1 464和1 464cm-1。在拉曼光谱中,两种有机配位化合物在1 004和1 008cm-1处归属为环呼吸振动峰、在1 617和1 615cm-1处归属为环伸缩振动峰、在720和720cm-1处归属为β(C—C)和ν(C—S)的复合振动峰,各自十分相似。     

Fourier Transform Infrared and Raman Spectra of Metal Halide Complexes of 3,5-Lutedine in Relation to Their Structures

Abstract

Fourier transform infrared (4000-200 cm¹) and Raman (3500-50 cm^?1) spectra are reported for metal(II) halide 3,5-lutidine (3,5-dimethylpyridine) complexes of the following stoichiometries: M(3,5L)₄X₂ M=Co or Ni, X=C1 or Br; M=Mn or Cu, X=Br; M=Cd, X=I; M(3,5L)₃X₂ M=Fe, X=C1; M=Cu, X=Br; Hg(3,5L) X₂ X=C1 or Br.

Vibrational assignments are given for all the observed bands. Some structure- spectra correlations are found. For a given series of isomorphous complexes the sum of the difference between the liquid and ligand values of the vibrational modes of 3,5-lutidine is found to increase in the order of the second ionization potentials of the metals. The frequency shifts are also found to depend on the halogen.