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 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 of hexaphenylcarbodiphosphorane

The displacement of tetrahydrofuran (THF) from W(CO)₅(THF) with hexaphenylcarbodiphosphorane yields a compound with a carbon-metal bond (CO)₅W C[P(C₆H₅)₃]₂. The in situ photolysis of tungsten hexacarbonyl and hexaphenylcarbodiphosphorane, however, yields a product (CO)₅W^?CC ⁺P(C₆H₅)₃. Ethylenebis(triphenylphosphine)platinum and hexaphenylcarbodiphosphorane in benzene yield a platinum containing heterocycle [(C₆H₅)₃P]₂$\text{PtC[ P(C}{}_6\text{H}{}_5\text{)}{}_3\text{]P}$-(C₆H₅)₃.     

Transition metal orotic acid complexes

Complexes of orotic acid with transition metals (Cu²⁺, Mn²⁺, VO²⁺, Zn²⁺, Hg²⁺, Cd²⁺, Fe³⁺, Cr³⁺, and Ag⁺) have been prepared and characterized by elemental, conductivity, magnetic measurements, i.r., n.m.r. and diffuse reflectance spectra. The ligand, in its monoanion form, coordinates through the carboxylic group to the metal. The Co²⁺ complex was also isolated under alkaline conditions and studied.     

Transition metal complexes of thioalcanamines

Summary Thioalcanamines, in which the N and S atoms are separated by two carbons, induce remarkable schistosomicidal behaviour in laboratory mice infected with the disease, a biological action which might arise from complexation of these potential ligands with metal ions. A study showed that it is possible to obtain both mono- and trimetallic complexes, and the latter can be either homo- or heterometallic.     

Transition metal complexes of Schiff base ligand based on 4,6-diacetyl resorcinol

Novel Schiff base ligand based on the condensation of 4,6-diacetyl resorcinol with 2-amino-4-methylthiazole in addition to its metal complexes with Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II), Zn (II) and Cd (II) ions have been synthesized. The structure, electronic properties, and thermal behaviour of Schiff base and its metal complexes have been studied by elemental analysis, mass, ¹H NMR, IR spectra, thermal analysis, and theoretically by density function theory. The ligand acted as mononegative bidentate (NO) ligand and all complexes showed octahedral geometry except Cu (II) showed tetrahedral geometry as indicated from the spectral and magnetic studies. The Cu (II), Zn (II) and Cd (II) complexes were non electrolytes while the rest of the complexes were electrolytes. The antibacterial plus anticancer activities of the parent Schiff base and its metal complexes were screened. In addition, the molecular docking study was performed to explore the possible ways for binding to Crystal Structure of Human Astrovirus capsid protein (5ibv) receptor.     

Syntheses and structural characterizations of three transition metal coordination complexes based on flexible 2,4-dichlorophenoxyacetate (2,4-DCP)

Three transition metal coordination complexes, {[Co(2,4-DCP)₂(μ ₂-H₂O)(H₂O)₂]?·?(H₂O)₂} _n (1), [Zn(2,4-DCP)(IN)] _n (2), and [Mn₂(2,4-DCP)₃(DMPY)₂(μ ₂-H₂O)(H₂O)]?·?(2,4-DCP)?·?0.2(H₂O) (3) (2,4-DCP?=?2,4-dichlorophenoxyacetate, IN?=?isonicotinate, DMPY?=?5,5′-dimethyl-2,2′-bipyridine), have been prepared under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a 1-D chain through cobalt and bridging water molecules with Co?···?Co distance of 4.028(2)?Å. Complex 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak hydrogen-bonding interactions. Complex 3 consists of discrete dinuclear cations, 2,4-DCP counter ions and free water molecules, which are assembled into a packing structure through π?···?π stacking of inversion-related DMPY ligands and hydrogen bonds. Magnetic susceptibility measurements show weak antiferromagnetic interactions in 1. The photoluminescence and lifetime of 2 in the solid state have also been studied.     

Transition metal complexes with hydrazides and hydrazones

A study was made of the thermal decomposition of octahedral Co(II) complexes of the type CoL_n X ₂·mH₂O, wheren=2 and 3,m=1,2 and 5 andX=Cl, Br, I, NCS, OAc andv ₂So₄, in both air and nitrogen atmospheres. It was established that the complexes are completely decomposed below 800° and CoO is formed as final product. The most probable decomposition mechanism was proposed. The tris(ligand) complexes were characterized by elemental analysis, and spectral and magnetic measurements, and all the data suggested the presence of a point group symmetry of type O_h.

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Zusammenfassung Sowohl in Luft als auch in Stickstoffatmosphäre wurde die thermische Zersetzung von oktaedrischen Co(II)-Komplexen der allgemeinen Formel CoL_nX₂· mH₂O (n=2 und 3,m=1, 2 und 5,X=Cl, Br, I, NCS, OAc und SO₄) untersucht. Es wurde festgestellt, daß sich die Komplexe unterhalb 800°C vollkommen zu CoO als Endprodukt zersetzen. Der wahrscheinlichste Zersetzungsmechanismus wurde unterbreitet. Die tris-Ligandenkomplexe wurden mittels Elementaranalyse sowie Spektral- und magnetischen Untersuchungen charakterisiert, alle Angaben deuten auf eine Punktsymmetriegruppe vom Typ Oh hin.

     

Metal complexes based on functionalized 4-hydroxypolyfluorocoumarins

4-Hydroxypolyfluorocoumarins containing an acetyl, 1-aminoethylidene, ethoxycarbonyl, or aminocarbonyl substituent on C³ form coordination compounds with transition and rare earth metal cations. Some coumarin derivatives and their metal complexes show fluorescent properties.     

Transition metal complexes of N-picolyl polyurethane

N-Picolyl polyurethanes (PUPY) were synthesized by nucleophilic substitution. The blends of these polyurethanes with various of transition metal chlorides [cobalt(II), nickel(II), and copper(II)] were studied by spectroscopic and thermal analysis. Ultraviolet-visible and infrared spectroscopic evidence indicates that a tetrahedral cobalt(II) complex with two pendent picolyl groups in the first-shell coordination sphere of Co²⁺ is formed in a series of blends with different molar ratio (from 10/1 to 2/1) of picolyl groups to cobalt(II) ions. According to the result of Small-Angle X-ray Scattering (SAXS), Differential Scanning Calorimetry (DSC), and Dynamic Mechanical Thermal Analysis (DMTA), coordination interaction between ligands in hard segments and metal ions provides a driving force for phase separation. The coordination strength of pyridine with Ni²⁺ is stronger than Co²⁺ and Cu²⁺. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1539–1546, 1998     

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 meet the rylenes

This Perspective highlights an emerging area of metal-organic chromophore science related to the photochemistry and photophysics of coordination compounds and organometallic structures covalently tethered to rylene (naphthalene-cored) imide and diimide scaffolds. This combination of molecules renders highly colourful structures producing an array of excited state behaviour and in some instances strongly aggregated self-assembled metal-organic architectures.     

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.

     

Transition metal complexes of 5-chlorouracil

Summary Complexes of 5-chlorouracil (5-ClU) (1) with 3d metal ions were characterized by elemental analysis, various spectroscopic methods (i.r., u.v. spectroscopy) and magnetic susceptibility measurements. The spectral evidence suggest that 5-ClU behaves as bidentate ligand in Ni^II, Cu^II, Zn^II, and Cd^II compounds, coordinating through its one carbonyl oxygen and one nitrogen whereas with Mn^II and Co^II it coordinates through the carbonyl oxygen only. The insolubility of the new complexes in organic solvents suggests that these are polymeric except for the Co^II complex which is soluble in pyridine. There is probable OH bridging in the Mn^II and Cu^II complexes and the 5-ClU may bridge in the rest.     

Transition metal complexes of γ-mercaptoalkylpiperidines

Summary Complexes with 1-methyl-3-(mercaptomethyl)piperidine (LH) and 1-methyl-2-(2-mercaptoethyl)piperidine (LH) Ligands in their thiolato (R), andN-protonated (HR) orN-methylated (MeR) zwitterionic form, of stoichiometry MR₂ (M=Ni, R=L or L; M=Cd, R=L), MR (M=Cu or Ag, R=L and L), [Ni(MeR)₂]I₂ · nH₂O (R=L, n=1; R=L, n=2), [Ni(HR)₂]X₂ (R=L or L, X=ClO₄; R=L, X=Br), and [Ag(HR)] ClO₄ (R=L) have been prepared and characterized. According to i.r. and electronic spectra, and magnetic measurements the nickel complexes exhibit polymeric frameworks built up from mercapto-bridged metal atoms in square-planar environments. Complexes with copper, silver, and cadmium exhibit similar polymeric arrangements through bridging sulphur atoms but with a different geometry at the metal centers, the first two being mainly linear, as anticipated, and the latter tetrahedral. In no case does coordinationvia nitrogen take place and therefore these ligands behave simply as mercaptides.