Transition metal complexes with pyrazole based ligands

The deaquation of two isostructural compounds of general formula [M(HL)₂(H₂O)₂](NO₃)₂ (M=Co, Ni, HL=3,5-dimethyl-1H-pyrazole-1-carboxamidine) is discussed in the view of their crystal and molecular structure. The compounds contain the same number and type of hydrogen bonds of the adjacent nitrate ions, only in the opposite orientation. On the basis of their deaquation pattern such a small difference may be detected, i.e., methods of thermal analysis are sensitive enough to show very small structural differences.     

Transition metal complexes based on thiophene-dithiolene ligands

The chemistry of transition metal dithiolene complexes based on thiophene-dithiolene ligands (TD) is reviewed, from the ligand synthesis and complex preparation to the molecular structure and solid state physical properties of different compounds based on them. The ligands considered are based mainly either on simple thiophene-dithiolates (α-tpdt = 2,3-thiophenedithiolate, dtpdt = 4,5-dihydro-2,3-thiophenedithiolate, and tpdt = 3,4-thiophenedithiolate), or in more extended and delocalised dithiolate ligands (α-tdt = 3-({5-[(2-cyanoethyl)thio]-2-thieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl}thio)propanenitrile and dtdt = 3-{5-[(2-cyanoethyl)thio]-2-(5,6-dihydrothieno[2,3-d][1,3]dithiol-2-ylidene-1,3-dithiol-4-yl)thio}propanenitrile) that besides the thiophenic ring also incorporates a fused TTF moiety. Dithiolene complexes based on ligands containing appended thiophenic units will also be briefly considered. The structural variability of these complexes that in addition to the usual square planar coordination geometry, M(TD)₂, can also present dimeric, [M(TD)₂]₂, or cluster structures such as [Cu₄(TD)₃] and [Ni₄(TD)₆], is addressed. The role of the thiophene group and its ability to enhance electronic delocalisation from the metal dithiolene core throughout the ligand and to establish solid state networks of S?S interactions is discussed. The importance of these complexes as useful building blocks to prepare molecular materials with very interesting magnetic and transport properties, ranging from metamagnets to Single Component Molecular Metals, is illustrated by different compounds based on them.     

Transition metal complexes with thiosemicarbazide-based ligands

Solvate complexes of UO ₂ ²⁺ andN(1), N(4)-bis(salicylidene)-S-methylisothiosemicarbazone, (H₂Me-L¹), of general formula [UO₂(Me-L¹)S] (S= H₂O, MeOH, EtOH, Py, DMF and DMSO) were synthesized. The methanolic UO ₂ ²⁺ ” adducts of N(1)-benzoylisopropylidene-N(4)-salicylidene-S-alkylisothiosemicarbazone, (H₂R-L²,R=Me, Prⁿ) of general formula [UO₂(R-L²)· MeOH], were also prepared. Thermal decomposition of the complexes was investigated in air and argon. The complexes decompose to α-U₃O₈ in air, while in argon the decomposition is not completed up to 1000 K. The temperature and the mechanism of decomposition of the complexes are a function of the solvent belonging to the inner coordination sphere.     

Transition metal complexes with thiosemicarbazide-based ligands

The thermal decomposition and spectroscopic (reflectance and IR spectra) characterization of the newly synthesized square-pyramidal dioxovanadium(V) complexes of the type NH₄[VO₂(L)] (L is the dianion of the terdentate ligands salicylaldehyde thiosemicarbazone (ONS), halogen-substituted salicylaldehyde and 2-hydroxy-1-naphthaldehyde S-methylisothiosemicarbazones (ONN)) are described.

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Zusammenfassung Es wird die thermische Zersetzung und spektroskopische Charakterisierung (Reflexionsvermögen und IR-Spektren) neu synthetisierter Dioxovanadium(V)-Komplexe der allgemeinen Formel NH₄[VO₂(L)] beschrieben, wobei L das Dianion des dreizahnigen Liganden Salicylaldehyd-thiosemicarbazon (ONS), halogensubstituiertes Salicylaldehyd- bzw. 2-Hydroxy-1-naphthaldehyd-S-methyl-isothiosemicarbazon (ONN) ist.

     

Formation constants for diarylthallium complexes with neutral ligands

Conclusions The coordinating ability of donor molecules with respect to di(m-tolyl)thallium chloride and di(pentafluorophenyl) thallium nitrate increase in the sequence: CH₃CN < DMFA < DMSO < Py < DMF< EDA. This similar to the Gutman donor number series, but somewhat different from the series for organomercury and organotin compounds. The complexing constants for the organothallium cations are several orders lower than those for the aryl compounds of mercury and tin.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1762–1765, August, 1976.     

Transition metal complexes with Girard reagent-based ligands

The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H₂SalGT]Cl (1), and two complexes [Cu(HSalGT)X₂]·H₂O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH₃)₃ group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption spectra.     

Conducting LB films based on metal complexes of sulphur donor ligands

Preliminary studies are reported on the film forming characteristics of compounds such as dialkyldimethylammonium-M (dmit)₂ and dialkyldimethylammonium-M (mnt)₂ where M = Ni, Pt or Pd. All materials investigated show good monolayer behaviour and deposit readily onto evaporated aluminium or gold films. This is confirmed by surface potential and FTIR measurements. The lateral conductivity of deposited films increases by many orders of magnitude when exposed to bromine vapour.     

Transition metal complexes with neutral and deprotonated malonamide

Summary New complexes of the general formulae [M(LH₂)₂Cl₂] (M = Mn, Fe, Co, Ni, Cu, Zn), [Mn(LH₂)₂X₂] (X = Br, I), [Cu(LH₂)₂Br₂], [Ni(LH₂)₂X₂] (X = Br, NCS, ONO₂), [Cu(LH₂)X₂]_n (X = Cl, Br), K₂[NiL₂]·2H₂O and K₂-[CuL₂]·H₂O, where LH₂ = malonamide, were isolated. The complexes were characterized by elemental analyses, X-ray powder patterns, magnetic susceptibilities and spectroscopic (variable-temperature ⁵⁷Fe-Mössbauer, e.s.r., u.v.-vis., i.r., far-i.r., Raman) studies. Monomeric trans pseudo-octahedral stereochemistries for the neutral 12 complexes and square planar structures of D _2h symmetry for the two ionic complexes are assigned in the solid state. Dimeric or polymeric five-coordinate structures are proposed for the 11 copper(II) compounds. LH₂ and L^2– behave as bidentate chelating ligands binding through oxygen and deprotonated nitrogen atoms, respectively. A detailed comparison of the studied complexes with the corresponding oxamide complexes is also presented.     

Gold complexes with potentially tri- and tetradentate phosphinothiolate ligands

Reactions of [Au(PPh3)Cl], (Bu4N)[AuCl4] and the organometallic gold complex [Au(damp-C1,N)Cl2] (damp- = 2-(N,N-dimethylaminomethyl)phenyl) with the potentially tri- and tetradentate proligands PhP(C6H3-SH-2-R-3)2 (H2L1a, R = SiMe3; H2L1b, R = H) and P(C6H4-SH-2)3 (H3L2) result in the formation of mono- or dinuclear gold complexes depending on the precursor used. Monomeric complexes of the type [AuL1Cl] are formed upon the reaction with [Au(damp-C1,N)Cl2], but small amounts of dinuclear [AuL1]2 complexes with gold in two different oxidation states, +1 and +3, have been isolated as side-products. The dinuclear compounds are obtained in better yields from [AuCl4]-. A dinuclear complex having two Au(III) centers can be isolated from the reaction of [Au(PPh3)Cl] with H3L2, whereas from the reaction with H2L1b the mononuclear [Au(Ph3P)HL1b] is obtained, which contains a three-coordinate gold atom. Comparatively short gold-gold distances have been found in the dinuclear complexes (2.978(2) and 3.434(1) A). They are indicative of weak gold-gold interactions, which is unusual for gold(III).     

Construction of mononuclear transition metal(II) complexes with bi- and tridentate,neutral hydrazone ligands with a quinoxaline hub

A series of Co(II), Ni(II), Cu(II), and Zn(II) complexes of bi- and tridentate hydrazones were prepared. Ligands L¹ and L² were synthesized by the condensation of 2-mercapto-3-hydrazinoquinoxaline with 2-hydroxy-3-formylquinoline and 3-acetylcoumarin, respectively. The compounds were characterized by various spectro-analytical techniques and magnetic moment studies. The complexes are found to be monomeric and non-electrolytes. In these complexes, [CuL¹Cl₂] has square pyramidal geometry and others have octahedral. The copper complexes are electrochemically active in the applied potential range.     

Electroanalytical chemistry of metal complexes with S-containing ligands

Summary The main types of electrochemical reactions of complexes in organic and mixed solvents are considered. Fast electrochemical reactions (k _s=n×10^–2 cm · s^–1) were used to reduce the minimal concentrations (c _min) in a.c. voltammetry. The role of pre- and post-chemical reactions in the formation of the analytical signal in extraction voltammetry is elucidated. The principles of the influence of the special structure of the complexes on their redox properties are determined using complexes of the transition metals with phosphorus dithioacids and bidentate heterocyclic amines. The features of the electrooxidation and electroreduction of inert complexes of the platinum metals with heterocyclic dithioacids and organic sulphides in nonaqueous media are discussed. The products of the electrochemical reaction of these compounds in protic media catalyze the hydrogen evolution on the mercury electrode. Kinetic data of the chelate formation are used for developing highly selective methods for the determination of the platinum metals with c _min=2×10^–9–5×10^–8 mol/l.

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Elektrochemische Reaktionen von Komplexen mit S-haltigen Liganden

     

Coordination complexes of silicon and germanium halides with neutral ligands

The coordination chemistry of silicon(IV) and (II) and germanium(IV) and (II) halides with neutral donor ligands from groups 15 (N, P or As) and 16 (O, S or Se) is reviewed; N-heterocyclic carbene complexes are also included. The focus is mainly on results published after 1990 and illustrates that significant recent developments have been made in the coordination chemistry of low-valent silicon and germanium halide complexes in particular; this is expected to pave the way for much new reaction chemistry both from a fundamental and application-driven perspective.     

Gold complexes containing organoselenium and organotellurium ligands

This article reviews the synthesis, structures, reactions and spectroscopic studies of gold complexes containing organoselenium and organotellurium ligands, i.e. compounds containing an Au–Se–C and Au–Te–C unit. The literature up to June 2009 has been covered. Appendix 1 lists important structural data of complexes which have been characterised by X-ray diffraction, whilst Appendix 2 contains a compilation of ⁷⁷Se and ¹²⁵Te NMR data for these compounds.     

Gold(I) complexes with tertiary phosphine sulfide ligands

Phosphine sulfides and their gold(I) complexes with general formula R₃P=S—Au—X (X = Cl^–, Br^– or CN^–) were prepared and characterized by elemental analyses, i.r. and ³¹P-n.m.r. spectroscopy. A decrease in the i.r. frequency of the P=S bond in the ligands upon complexation, is indicative of S coordination to gold (I). The ³¹P-n.m.r. spectra revealed that electronegativity of the substituents and angles between them were the two most important factors influencing the ³¹P-n.m.r. chemical shifts. The phosphorus resonance was observed to be more downfield in alkyl substituted phosphine sulfides as compared to the aryl substituted phosphine sulfides. Ligand scrambling in the Cy₃P=S—Au—CN complex in solution, to form [(Cy₃P=S)₂Au]⁺ and [Au(CN)₂]^–, was investigated by ¹³C and ¹⁵N-n.m.r. spectroscopy. Equilibrium constants (K _eq) for scrambling of the Cy₃P=S—Au—CN complex and for its analogue, Cy₃P=Se—Au—CN were measured by integrating the ¹³C-n.m.r. at 297 K and were found to be 0.147 and 1.81 respectively.     

Transition metal complexes of pyrazinecarboxylic acids with neutral hydrazine as a ligand

New divalent Co, Ni, Zn and Cd pyrazinecarboxylate hydrazinates of the formulae M(pyzCOO)₂·nN₂H₄·xH₂O and Mpyz(COO)₂·N₂H₄·xH₂O obtained by the reaction of respective metal nitrate hydrates with 2-pyrazinecarboxylic (HpyzCOO)/2,3-pyrazinedicarboxylic (H₂pyz(COO)₂) acid and hydrazine hydrate have been characterized on the basis of analytical, spectroscopic (electronic and infrared), thermal and X-ray powder diffraction studies. The electronic spectroscopic data suggest that the cobalt and nickel complexes are of spin-free (high-spin) type with octahedral geometry. The IR absorption bands of N-N stretching in the range 980-972 cm^-1 unambiguously prove the bidentate bridging nature of the N₂H₄ ligand. The hydrazinate complexes of 2,3-pyrazinedicarboxylate lose hydrazine molecule exothermally, whereas 2-pyrazinecarboxylate compounds lose the same endothermally. Further, all the complexes undergo endothermic (dehydration and/or dehydrazination) followed by exothermic decomposition except the Zn and Cd complexes of 2,3-pyrazinedicarboxylate, which show only exothermic decomposition. In order to know the isomorphic nature among the complexes, the X-ray powder patterns have been compared.     

Gold(I) complexes with thiolate and triphenylphosphine ligands

The reaction of [AuCl(PPh₃)] with Pb(SR)₂(R = C₂H₅, C₆H₅, CH₂C₆H₅, C₆F₅, C₆H₂Me₃-2,4,6, Prⁱ and Bu^t) provides a clean method to obtain complexes of the type [Au(SR)(PPh₃)] in good yields. The new compounds have been characterized by IR, ¹H, ³¹P, ¹⁹F and ³¹C NMR. A study by FAB mass spectrometry indicates that an ion-molecule aggregation process takes place.     

Polynuclear metal complexes incorporating hydrido-phosphido ligands

Addition of phosphines to the coordinatively unsaturated species (Cp)₂M₂(CO)₄ (M = Mo, W) and H₂Os₃(CO)₁₀ yield a series of products incorporating terminal phosphine along with bridging and capping phosphido ligands formed via insertion into PH bonds. The complexes were characterised by ¹H and ³¹P NMR spectroscopy and mass spectrometry.