New palladium(II) complexes with pyrazole ligands

The pyrazole ligand 3,5-dimethyl-4-iodopyrazole (HdmIPz) has been used to obtain a series of palladium(II) complexes (1–4) of the type [PdX₂(HdmIPz)₂] {X = Cl⁻ (1); Br⁻ (2); I⁻ (3); SCN⁻ (4)}. All compounds have been isolated, purified, and characterized by means of elemental analysis, IR spectroscopy, ¹H and ¹³C{¹H}-NMR experiments, differential thermal analysis (DTA), and thermogravimetry (TG). The TG/DTA curves showed that the compounds released ligands in the temperature range 137–605 °C, yielding metallic palladium as final residue. The complexes and the ligand together with cisplatin have been tested in vitro by MTT assay for their cytotoxicity against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07).     

Orotic acid complexes of Co(II), Ni(II), Zn(II) and Cd(II) with imidazole

The [Co(HOr)(H₂O)₂(im)₂] (1), [Ni(HOr)(H₂O)₂(im)₂] (2), [Zn(H₂O)₂(im)₄](H₂Or)₂ (3) and [Cd(HOr)(H₂O)(im)₃] (4) complexes (H₃Or: orotic acid, im: imidazole) were synthesized and characterized by elemental analysis, magnetic and conductance measurements, UV-vis and IR spectra. The thermal behaviour of the complexes was also studied by simultaneous thermal analysis techniques (TG, DTG and DTA). The orotate ligand (HOr²⁻) coordinated to the Co(II), Ni(II) and Cd(II) ions are chelated to the deprotonated pyrimidine nitrogen (N₍₃₎) and the carboxylate oxygen, while do not coordinate to the Zn(II) ion is present as a counter-ion (H₂Or⁻). The first thermal decomposition process of all the complexes is endothermic deaquation. This stage is followed by partially (or completely) decomposition of the imidazole and orotate ligands. In the later stage, the remained organic residue exothermically burns. On the basis of the first DTG_max, the thermal stability of the complexes follows order: 2, 176°C>1, 162°C>4, 155°C>3, 117°C in static air atmosphere. The final decomposition products which identified by IR spectroscopy were the corresponding metal oxides.     

Thermal and spectroscopic investigation on N,N-dimethylbenzylamine based cyclopalladated compounds containing isonicotinamide

Synthesis, spectroscopic characterization and thermal analysis of the [Pd(dmba)(Cl)(iso)] (1), [Pd(dmba)(NCO)(iso)] (2), [Pd(dmba)(N₃)(iso)] (3) and [Pd(dmba)(Br)(iso)] (4) (dmba = N,N′-dimethylbenzylamine; iso = isonicotinamide) compounds are described in this work. The complexes were investigated by infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TG) and the residues of the thermal decomposition were identified as Pd^o by X-ray powder diffraction. The thermal stability order of the complexes varied as [Pd(dmba)(Cl)(iso)] (1) > [Pd(dmba)(Br)(iso)] (4) > [Pd(dmba)(NCO)(iso)] (2) > [Pd(dmba)(N₃)(iso)] (3).     

Thermal study of mononuclear Pd(II) complexes of the type [Pd(X)<Subscript>2</Subscript>(Rtu)(PPh<Subscript>3</Subscript>)] (X = Cl,SCN; Rtu = <Emphasis Type="Italic">N</Emphasis>-methylthiourea, <Emphasis Type="Italic">N</Emphasis>-phenylthiourea)

The synthesis, spectroscopic characterization, and thermal analysis of the compounds [Pd(X)₂(mtu)(PPh₃)] (X = Cl⁻ (1), SCN⁻ (2); mtu = N-methylthiourea; PPh₃ = triphenylphosphine) and [Pd(X)₂(phtu)(PPh₃)] (X = Cl⁻ (3), SCN⁻ (4); phtu = N-phenylthiourea) are described. The thermal decomposition of the compounds occurs in two, three, or four stages and the final decomposition products were identified as Pd⁰ by X-ray powder diffraction. The thermal stability order of the complexes is 4 > 3>2 > 1.     

Mono and dinuclear Pd(II) complexes with pyrazole and imidazole-type ligands Synthesis, characterization and thermal behaviour

The cyanate-bridged cyclopalladated compound [Pd(C²,N-dmba)(μ-NCO)]₂ (dmba=N,N-dimethylbenzylamine) reacts in acetone with pyrazole (pz), 3,5-dimethylpyrazole (dmpz), imidazole (imz) and 2-methylimidazole (mimz) to give [Pd₂(C²,N-dmba)₂(μ-NCO)(μ-pz)] (1), [Pd₂(C²,N-dmba)₂(μ-NCO)(μ-dmpz)] (2), [Pd(C²,N-dmba)(NCO)(imz)] (3) and [Pd(C²,N-dmba)(NCO)(mimz)] (4), respectively. The compounds were characterized by elemental analysis, IR spectroscopy and TG. The thermal decomposition of the compounds occurs in three consecutive steps and the final decomposition products were identified as Pd(0) by X-ray powder diffraction. The thermal stability order of the complexes is 2>3>1>4.     

Study on the thermal behavior of the complexes of the type [PdX<Subscript>2</Subscript>(tdmPz)] (X = Cl<Superscript>−</Superscript>, Br<Superscript>−</Superscript>, I<Superscript>−</Superscript>, SCN<Superscript>−</Superscript>)

Four new mononuclear Pd(II) complexes of the type [PdX₂(tdmPz)] {X = Cl⁻ (1); Br⁻ (2); I⁻ (3); SCN⁻ (4); tdmPz = 1-thiocarbamoyl-3,5-dimethylpyrazole} have been synthesized and characterized by elemental analysis, IR spectroscopy, ¹H and ¹³C{¹H}-NMR experiments. The thermal behavior of the complexes 1–4 has been investigated by means of thermogravimetry (TG) and differential thermal analysis (DTA). From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 3 < 4 ≡ 2 < 1. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.     

Thermal behaviour of new Cu(II) complexes with Schiff bases functionalised with 1,3,5-triazine moieties as potential antibacterial agents

New complexes of type [Cu(L¹)₂(OH₂)]·4H₂O (1), [Cu(L²)(OH₂)]·0.5H₂O (2) and [Cu₃(L³)₂(OH₂)₃]·0.5H₂O (3) were synthesized by [1 + 1], [1 + 2] and [1 + 3], respectively, template condensation of 2,4,6-triamino-1,3,5-triazine and salicylic aldehyde in the presence of copper(II). The features of complexes have been established from microanalytical, IR and UV–Vis data. The thermal analyses have evidenced the thermal intervals of stability and also the accompanying thermodynamic effects. Processes as water elimination and oxidative degradation of the organic ligands were observed. After water elimination, complexes revealed a similar thermal behaviour. The final product of decomposition was copper(II) oxide as powder X-ray diffraction indicated.     

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.     

Phase transformation in a nanostructured M300 maraging steel obtained by SPS of mechanically alloyed powders

New complexes of type [Cu(HTBG)₂]Cl₂ (1), [Cu(TBG)₂]·3H₂O (2) and [CuL]·nH₂O (3) L:L¹, n = 2 and (4) L:L², n = 1 (HTBG: 2-tolylbiguanide, L¹ and L²: ligands resulted from 2-tolylbiguanide, ammonia/hydrazine and formaldehyde one pot condensation) were synthesised and characterised. The features of complexes have been assigned from microanalytical, IR and UV–Vis data. Redox behaviour was established by cyclic voltammetry. The in vitro qualitative and quantitative antimicrobial activity assays showed that the complexes exhibited variable antimicrobial activity against Gram-negative and Gram-positive strains isolated from the hospital environment. The thermal analyses have evidenced the thermal intervals of stability and also the thermodynamic effects that accompany them. After water elimination, complexes have a similar thermal behaviour. Processes as water elimination, melting, chloride anion removal as well as oxidative degradation of the organic ligands were observed. The final product of decomposition was copper (II) oxide.     

Synthesis,characterization, thermal studies,and DFT calculations on Pd(II) complexes containing <Emphasis Type="Italic">N</Emphasis>-methylbenzylamine

This work describes the synthesis, characterization, and the thermal behavior investigation of four palladium(II) complexes with general formulae [PdX₂(mba)₂], in which mba = N-methylbenzylamine and X = OAc⁻ (1), Cl⁻ (2), Br⁻ (3) or I⁻ (4). The complexes were characterized by elemental analysis, infrared vibrational spectroscopy, and ¹H nuclear magnetic resonance. The stoichiometry of the complexes was established by means of elemental analysis and thermogravimetry (TG). TG/DTA curves showed that the thermodecomposition of the four complexes occurred in 3–4 steps, leading to metallic palladium as final residue. The palladium content found in all curves was in agreement with the mass percentages calculated for the complexes. The following thermal stability sequence was found: 3 > 2 > 4 > 1. The geometry optimization of 1, 2, 3, and 4, calculated using the DFT/B3LYP method, yielded a slightly distorted square planar environment around the Pd(II) ion made by two anionic groups and two nitrogen atoms from the mba ligand (N1 and N2), in a trans-relationship.     

Nuclease activity of redox/non-redox active binuclear transition metal mixed-polypyridine complexes: [M2(1,4-tpbd)(diimine)2(H2O)2]4+, M = Zn,Co, Ni,Cd, diimine = phen,bpy, dafo

Seven new transition metal complexes formulated as [M₂(1,4-tpbd)(diimine)₂(H₂O)₂]⁴⁺ [M = Zn, Co, Ni, Cd; 1,4-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,4-diamine; diimine is a N,N-donor heterocyclic base like 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 4,5-diazafluoren-9-one (dafo)] have been synthesized and structurally characterized by X-ray crystallography: [Zn₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (1), [Zn₂(1,4-tpbd)(bpy)₂(H₂O)₂]⁴⁺ (2), [Co₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (3), [Ni₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (4), [Ni₂(1,4-tpbd)(bpy)₂(H₂O)₂]⁴⁺ (5), [Ni₂(1,4-tpbd)(dafo)₂(H₂O)₂]⁴⁺ (6) and [Cd₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (7). Single crystal diffraction reveals that the metals in the complexes are all in a distorted octahedral geometry. The interactions of the seven complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescence, circular dichroism spectroscopy and viscosity measurements. The apparent binding constants (K_app) are calculated to be 5.2?×?10⁵ M^?1 for 1, 1.05?×?10⁵ M^?1 for 2, 5.76?×?10⁵ M^?1 for 3, 4.57?×?10⁵ M^?1 for 4, 1.29?×?10⁵ M^?1 for 5, 1.7?×?10⁵ M^?1 for 6, 2.53?×?10⁵ M^?1 for 7, the binding propensity to the calf thymus DNA in the order: 3 (Co-phen) > 1 (Zn-phen) > 4 (Ni-phen) > 7 (Cd-phen) > 6 (Ni-dafo) > 5 (Ni-bpy) > 2 (Zn-bpy). Furthermore, these complexes display efficient oxidative cleavage of supercoiled DNA; the Zn(II)/H₂O₂ and Cd(II)/H₂O₂ systems efficiently cleave DNA attributed to the peroxide ion coordinated to the Zn(II) and Cd(II), which enhanced their nucleophilicity, this is rare.     

Thermoanalytical studies of oxovanadium(IV)hydroxamate complexes

The thermal decomposition behavior of oxovanadium(IV)hydroxamate complexes of composition [VO(acac)(C₆H₅C(O)NHO)] (I), [VO(C₆H₅C(O)NHO)₂] (II), [VO(acac)(4-ClC₆H₄C(O)NHO)] (III), [VO(4-ClC₆H₄C(O)NHO)₂] (IV) (where acac = (CH₃COCHCOCH₃ ^–) synthesized from the reactions of VO(acac)₂ with equi- and bimolar amounts of potassium benzohydroxamate and potassium 4-chlorobenzohydroxamate in THF + MeOH solvent medium has been studied by TG and DTA techniques. TG curves indicated that complexes I, II, and IV undergo decomposition in single step to yield VO₂ as the final residue, while complex III decomposes in two steps to yield VO(acac) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stability for the complexes has been inferred as IV > I > III > II.     

Synthesis,crystal structure,and luminescent properties of metal complexes bearing 2,6-pyridine-diacylhydrazide ligands: supramolecular assemblies via intermolecular interactions

Four metal complexes of N,N′-bis(salicyl)-2,6-pyridine-dicarbohydrazide ligand (H₆L), [Co^II(H₄L)(H₂O)₂]·2DMF (1), [Zn^II(H₄L)(H₂O)₂]·2DMF (2), [Cd^II(H₄L)(Py)₂]·DMF·Py (3), and [Co^IICo₂^III(H₄L)₄(H₂O)₄]·DMF·H₂O (4), were synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis. Structural studies revealed that complexes 1–3 present discrete mononuclear structures and complex 4 displays a centrosymmetric mixed-valence trinuclear structure. All four complexes are further extended into interesting two- or three-dimensional supramolecular frameworks. The luminescent properties of 2 and 3 were studied, which show emissions with maxima at 485 nm upon excitation at 396 nm for 2 and 476 nm upon excitation at 397 nm for 3, respectively.     

Effects of substituent on the DNA-binding of ruthenium(II) complexes containing asymmetric tridentate intercalative ligands

Three novel unsymmetric tridentate ligands, namely, ptmi (ptmi = 3-(1,10-phenanthroline-2-yl)-as-triazino[5,6-f]-5-methoxyisatin), pti (pti = 3-(1,10-phenanthroline-2-yl)-as-triazino-[5,6-f]isatin), ptni (ptni = 3-(1,10-phenanthroline-2-yl)-as-triazino[5,6-f]-5-nitroisatin), and their complexes [Ru(tpy)(ptmi)](ClO₄)₂ (tpy = 2,2′:6′,2″-terpyridine) (1), [Ru(tpy)(pti)](ClO₄)₂ (2), and [Ru(tpy)(ptni)](ClO₄)₂ (3) were prepared and characterized by elemental analysis, ¹H NMR, ES–MS. The electrochemical behaviors were studied by cyclic voltammetry. The DNA-binding properties of these complexes were investigated by the spectroscopic method, viscosity measurements, and thermal denaturation. Theoretical studies on these complexes were also performed with the density functional theory (DFT) method. The experimental results showed that these complexes bind to calf thymus (CT-DNA) in an intercalative mode. The order of DNA-binding affinities (A) of these complexes is A(1) < A(2) < A(3). The trend in the DNA-binding affinities of this series of complexes can be reasonably explained by the DFT calculations.     

Synthesis,crystal structure and characterization of a series of complexes constructed from coordinated Lanthanides(III) and the heteropolyanion [SiMo12O40]4−

The reaction of α-[SiMo₁₂O₄₀]^4? with trivalent cations Ln³⁺ and N-methyl-2-pyrrolidone leads to a series of complexes of formula [Ln(NMP)₄(H₂O) _n ]H[SiMo₁₂O₄₀]?·?2NMP?·?mH₂O [where Ln?=?La (1), Pr (2), Nd (3), Sm (4), Gd (5), n?=?4, Ln?=?Dy (6), Er (7), n?=?3. NMP?=?N-methyl-2-pyrrolidone]. The syntheses, X-ray crystal structures, IR, and ESR spectra and thermal properties of the complexes 1, 2, 4, 6, 7 have been reported previously. Here, we report X-ray crystal structures, IR, UV, ESR spectra and thermal properties of the complexes [Nd(NMP)₄(H₂O)₄]H[SiMo₁₂O₄₀]?·?2NMP?·?1.5H₂O (3), and [Gd(NMP)₄(H₂O)₄]H[SiMo₁₂O₄₀]?·?2NMP?·?H₂O (5). In addition, the electrochemical behaviour of this series of complexes in aqueous solution and aqueous-organic solution has been investigated and systematic comparisons have been made. All these complexes exhibit successive reduction process of the Mo atoms.     

Platinum complexes with diamino-substituted phosphorus ligands: Synthesis,characterization, and their reactivity with a Lewis acid

Reaction of dialkyl- or diaryl-platinum complexes PtR₂(cod) (cod = η², η²-1,5-cyclooctadiene, R = Me, p-tol) with diamino-substituted phosphorus ligands P(NMeCH₂)₂(R′) (R′ = OMe, NEt₂) produced neutral complexes, cis-[Pt(R)₂{P(NMeCH₂)₂(R′)}₂]. On the other hand, reaction of dihalogeno platinum complex PtX₂(cod) (X = Cl, I) with P(NMeCH₂)₂(OMe) yielded a cationic complex [PtX{P(NMeCH₂)₂(OMe)}₃]X. A platinum complex having both methyl and halogeno ligands, PtMeX(cod), reacted with P(NMeCH₂)₂(OMe) to give a cationic methyl complex [PtMe{P(NMeCH₂)₂(OMe)}₃]X, by contrast, it reacted with P(NMeCH₂)₂(NEt₂) to yield a neutral methyl complex [PtMeX{P(NMeCH₂)₂(NEt₂)}₂]. Reaction of [PtMe{P(NMeCH₂)₂(OMe)}₃]X with BF₃·OEt₂ and then NaBPh₄ afforded [PtX{P(NMeCH₂)₂(OMe)}₃]BPh₄, showing preferential Me group abstraction on the Pt center rather than the OMe abstraction on the phosphorus atom, followed by the coordination of X to the Pt center. All new complexes were fully characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR measurements and elemental analyses. In addition, structures of several complexes were determined by single crystal X-ray diffraction studies.     

Iron Pentacarbonyl Promoted Addition of CO and MeOH to 1,4-Disubstituted-1,3-butadiyne and Formation of Vinylallyl and Butatriene Ligand Systems

Abstract  Photochemical reaction of methanol solution containing 1,4-diferrocenyl- or 1,4-diphenyl-1,3-butadiynes and iron pentacarbonyl into which CO was constantly bubbled, yielded diiron hexacarbonyl complexes of cumulene ligand systems, [η¹: η³-{RCHC₂CR(COOMe)}Fe₂(CO)₆] (1; E, R = Fc, 2; Z, R = Fc, 5; E, R = Ph, 6; Z, R = Ph) and [η³: η³-{RCHC₂CR(COOMe)}Fe₂(CO)₆] (3; E, R = Fc, 7; E, R = Ph), formed by 1,4-addition of –COOMe and –H to the butadiynes. Additionally, diferrole, [Fe(CO)₄{C(O)CC(Fc)C(O)}₂],4 was obtained in minor quantity. Compounds 1, 2, 5 and 6 contain vinylallyl carbon framework which is stabilized by MeOC=O → Fe bond along with η¹: η³ coordinated Fe₂(CO)₆ unit. Compounds 3 and 7 contain butatriene units which are stabilized by η³: η³ coordinated Fe₂(CO)₆ unit. Characterization of the new compounds was carried out by IR and ¹H and ¹³C NMR spectroscopy and by mass spectrometry. Molecular structures of 2–7 were established by single crystal X-ray diffraction methods. Graphical Abstract  Diiron hexacarbonyl complexes of cumulene ligand systems, [η¹: η³ {RCHC₂CR(COOMe)}] (1; E, R = Fc, 2; Z, R = Fc, 5; E, R = Ph, 6; Z, R = Ph) and [η³: η³-{RCHC₂CR(COOMe)}] (3; E, R = Fc, 7; E, R = Ph) were obtained from photochemical reactions between Fe(CO)₅, CO and methanol. Yield of the minor product, the diferrole, 4, was improved when the photoreaction was carried out in hexane in place of methanol      

Synthesis and characterization of palladium(II) complexes of thioureas. X-ray structures of [Pd( N , N ′-dimethylthiourea)4]Cl2?·?2H2O and [Pd(tetramethylthiourea)4]Cl2

Palladium(II) complexes of thiones having the general formula [Pd(L)₄]Cl₂, where L = thiourea (Tu), methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu), and tetramethylthiourea (Tmtu) were prepared by reacting K₂[PdCl₄] with the corresponding thiones. The complexes have been characterized by elemental analysis, IR and NMR spectroscopy, and two of these, [Pd(Dmtu)₄]Cl₂ · 2H₂O (1) and [Pd(Tmtu)₄]Cl₂ (2), by X-ray crystallography. An upfield shift in the >C=S resonance of thiones in ¹³C NMR and downfield shift in N–H resonance in ¹H NMR are consistent in showing sulfur coordination with palladium(II). The crystal structures of the complexes show a square-planar coordination environment around the Pd(II) ions with the average cis and trans S–Pd–S bond angles of 89.64° and 173.48°, respectively. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. An erratum to this article can be found at     

Structure and properties of μ<Subscript>2</Subscript>-<Emphasis Type="Italic">S</Emphasis>-[bis(benzenethiolato)tetranitrosyldiiron] in solution

Dinuclear iron tetranitrosyl complex with the composition [Fe₂(SPh)₂(NO)₄] (1) was synthesized and its single crystals and polycrystals were studied by X-ray diffraction, IR spectroscopy, and elemental analysis. The decomposition products of complex 1 were investigated by electrochemical method and mass spectrometry. The mass spectrum of a solution of complex 1 shows two groups of ions: the primary decomposition products of 1 in solution (the complex ions [Fe(SPh)(NO)₂(NO₂)]⁻, [Fe(SPh)₂(NO)]⁻, and [Fe(SPh)₂(NO)₂]⁻) and a series of the ions [FeO₂ + n(NO)]⁻ and [FeO₃ + n(NO)]⁻ (n = 0–4), which are formed in secondary reactions. The structures of the complexes, which were formed through the Fe-NO bond dissociation and the replacement of the NO ligand by aqua and oxygen ligands in complex 1, and the structure of the complex [FeO₃]⁻ were studied by quantum chemical modeling.     

Thermal studies of some biologically active oxovanadium(IV) complexes containing 8-hydroxyquinolinate and hydroxamate ligands

The thermal decomposition behaviours of oxovanadium(IV)hydroxamate complexes of composition [VO(Q)_2?n(HL^1,2)_n]: [VO(C₉H₆ON)(C₆H₄(OH)(CO)NHO)] (I), [VO(C₆H₄(OH)(CO)NHO)₂] (II), [VO(C₉H₆ON)(C₆H₄(OH)(5-Cl)(CO)NHO)] (III), and [VO(C₆H₄(OH)(5-Cl)(CO)NHO)₂] (IV) (where Q?=?C₉H₆NO^? 8-hydroxyquinolinate ion; HL¹?=?[C₆H₄(OH)CONHO]^? salicylhydroxamate ion; HL²?=?[C₆H₃(OH)(5-Cl)CONHO]^? 5-chlorosalicylhydroxamate ion; n?=?1 and 2), which are synthesised by the reactions of [VO(Q)₂] with predetermined molar ratios of potassium salicylhydroxamate and potassium 5-chlorosalicylhydroxamate in THF?+?MeOH solvent medium, have been studied by TG and DTA techniques. Thermograms indicate that complexes (I) and (III) undergo single-step decomposition, while complexes (II) and (IV) decompose in two steps to yield VO(HL^1,2) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stabilities for the complexes has been inferred as III?>?I > II?>?IV.