Syntheses, crystal structures and magnetic properties of trinuclear and [3 × 1 + 1 × 2] pentanuclear complexes derived from a compartmental ligand: Role of solvent on nuclearity and number of components

Reaction of [Cu^IIL⊂(H₂O)] (H₂L = N,N′-ethylenebis(3-ethoxysalicylaldimine)) with nickel(II) perchlorate in 1:1 ratio in acetone produces the trinuclear compound [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂ (1). On the other hand, on changing the solvent from acetone to methanol, reaction of the same reactants in same ratio produces the pentametallic compound [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂·2[Cu^IIL⊂(H₂O)]·2MeOH (2A), which loses solvated methanol molecules immediately after its isolation to form [(Cu^IIL)₂Ni^II(H₂O)₂](ClO₄)₂·2[Cu^IIL⊂(H₂O)] (2B). Clearly, formation of 1 versus 2A and 2B is solvent dependent. Crystal structures of 1 and 2A have been determined. Interestingly, compound 2A is a [3 × 1 + 1 × 2] cocrystal. The cryomagnetic profiles of 1 and 2B indicate that the two pairs of copper(II)···nickel(II) ions in the trinuclear cores in both the complexes are coupled by almost identical moderate antiferromagnetic interaction (J = −22.8 cm⁻¹ for 1 and −26.0 cm⁻¹ for 2B).     

Synthesis, characterization, crystal structures and magnetic properties of dissymmetrical double schiff base heterotrinuclear complexes: [CuL(H2O)CoCuL] · H2O · CH3OH and [(CuL)2Ni] · 2H2O

A dissymmetrical double Schiff base Cu(II) mononuclear complex: CuHL (1) (where H₃L is N-3-carboxylsalicylidene-N^′-salicylaldehyde-1,2-diaminoethane) and two trinuclear complexes: [CuL(H₂O)CoCuL] · H₂O · CH₃OH (2) and [(CuL)₂Ni] · 2H₂O (3) have been synthesized and characterized by means of elemental analyses, IR and electronic spectra. The crystal structures of two heterotrinucler complexes were determined by X-ray analysis. Each dissymmetrical cell unit of the complex 2 contains two heterotrinucler neutral molecules. In each neutral molecule, the central Co²⁺ ion is located at the site of O₆ with a distorted octahedral geometry and one terminal Cu²⁺ ion at the four-coordination site of N₂O₂, but the other one at the square-pyramidal environment of N₂O₃. Each dissymmetrical unit of the complex 3 contains a heterotrinucler neutral molecule, whose structure is similar to that of 2 except two terminal Cu²⁺ ions both at the inner site of N₂O₂. The magnetic properties of two heterotrinucler complexes have been determined in the temperature range of 5-300 K, which indicate that the interaction between the central Co²⁺ ion or Ni²⁺ ion and the outer Cu²⁺ ions is antiferromagnetic. The exchange integrals are equal to −26.2 cm⁻¹ for 2 and −50.6 cm⁻¹ for 3.     

{Ru-NO} and {Ru-NO} configurations in [Ru(trpy)(tmp)(NO)] (trpy = 2,2:6′,2′′-terpyridine, tmp = 3,4,7,8-tetramethyl-1,10-phenanthroline): An experimental and theoretical investigation

The ruthenium-nitrosyl complexes [Ru^II(trpy)(tmp)(NO⁺)](ClO₄)₃ ([4](ClO₄)₃) and [Ru^II(trpy)(tmp)(NO)](ClO₄)₂ ([5](ClO₄)₂) with {Ru-NO}⁶ and {Ru-NO}⁷ configurations, respectively (trpy = 2,2′:6′,2′′-terpyridine, tmp = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been isotaled. The nitrosyl complexes [4]³⁺ and [5]²⁺ have been generated by following a stepwise synthetic procedure: [Ru^II(trpy)(tmp)(X)]ⁿ, X/n = Cl/+ (1⁺) → CH₃CN/2+ (2²⁺) → NO₂/+ (3⁺) → NO⁺/3+ (4³⁺) → NO/2+ (5²⁺). The single-crystal X-ray structures of two precursor complexes [1]ClO₄ and [3]ClO₄ have been determined. The DFT optimized structures of 4³⁺ and 5²⁺ suggest that the Ru-N-O geometries in the complexes are linear (177.9°) and bent (141.4°), respectively. The nitrosyl complexes with linear (4³⁺) and bent (5²⁺) geometries exhibit ν(NO) frequencies at 1935 cm⁻¹ (DFT: 1993 cm⁻¹) and 1635 cm⁻¹ (DFT: 1684 cm⁻¹), respectively. Complex 4³⁺ undergoes two successive reductions at 0.25 V (reversible) and −0.48 V (irreversible) versus SCE involving the redox active NO function, Ru^II-NO⁺ ? Ru^II-NO and Ru^II-NO → Ru^II-NO⁻, respectively, besides the reductions of trpy and tmp at more negative potentials. The DFT calculations on the optimized 4³⁺ suggest that LUMO and LUMO+1 are dominated by NO⁺ based orbitals of around 65% contribution along with partial metal contribution of ∼25% due to (dπ)Ru^II → π∗(NO⁺) back-bonding. The lowest energy transitions in 4³⁺ and 5²⁺ at 360 nm and 467 nm in CH₃CN (TD-DFT: 364 and 459 nm) have been attributed to mixed MLLCT transitions of tmp(π) → NO⁺(π∗), Ru(dπ)/tmp(π) → NO⁺(π^∗) and Ru(dπ)/NO(π) → trpy(π^∗), respectively. The paramagnetic reduced species 5²⁺ exhibits an anisotropic EPR spectrum with g₁ = 2.018, g₂ = 1.994, g₃ = 1.880 (〈g〉 = 1.965 and Δg = 0.138) in CH₃CN, along with ¹⁴N (I = 1) hyperfine coupling constant, A2 = 35 G at 110 K due to partial metal contribution in the singly occupied molecular orbital (DFT:SOMO:Ru (34%) and NO (53%)). Consequently, Mulliken spin distributions in 5²⁺ are calculated as 0.115 for Ru and 0.855 for NO (N, 0.527; O, 0.328). The reaction of moderately electrophilic nitrosyl center in 4³⁺ with the nucleophile, OH⁻ yields the nitro precursor, 3⁺ with the second-order rate constant value of 1.7 × 10⁻¹ M⁻¹ s⁻¹ at 298 K in CH₃CN-H₂O (10:1). On exposure to light (Xenon 350 W lamp) both the nitrosyl species, 4³⁺ ({Ru^II-NO⁺}) and 5²⁺ ({Ru^II-NO}) undergo photolytic Ru-NO bond cleavage process but with a widely varying k_NO, s⁻¹ (t_1/2, s) of 1.56 × 10⁻¹(4.4) and 0.011 × 10⁻¹(630), respectively.     

Effect of the central metal ion on the cleavage of DNA by [M(TPA)Cl]ClO4 complexes (M = Co, Cu and Zn, TPA = tris(2-pyridylmethyl)amine): An efficient artificial nuclease for DNA cleavage

[M(TPA)Cl]ClO₄·nH₂O complexes (1: M = Co^II, n = 0; 2: M = Cu^II, n = ½; 3: M = Zn^II, n = 0) where TPA = tris(2-pyridylmethyl)amine, were synthesized and structurally characterized. The molecular structure of [Cu(TPA)Cl]ClO₄·½H₂O was determined by single crystal X-ray crystallography. In aqueous solution, the complex ions [M(TPA)Cl]⁺ (M = Co^II or Cu^II) are hydrolyzed to the corresponding aqua species [M(TPA)(H₂O)]²⁺. In contrast to the TBP [Cu(TPA)(H₂O)]²⁺, the corresponding TBP cobalt(II) species showed severe distortion towards tetrahedral geometry. The interactions of the three complexes with DNA have been investigated at pH 7.0 (1.0 mM Tris-Cl buffer) and 37 °C. Significant DNA cleavages were obtained for complexes 1 and 2, whereas complex 3 did not show any detectable cleavage for DNA. Under pseudo Michaelis-Menten kinetic conditions, the kinetic parameters k_cat and K_M were determined as k_cat = 6.59 h⁻¹ and K_M = 2.20 × 10⁻⁴ M for 1 and the corresponding parameters for 2 are k_cat = 5.7 × 10⁻² h⁻¹ and K_M = 6.9 × 10⁻⁵ M, and the reactivity of the complexes in promoting the cleavage of DNA decreases in the order 1 > 2 ? 3. The rate enhancements for the DNA cleavage by 1 and 2 correspond to 1.8 × 10⁸ and 1.6 × 10⁶, respectively, over the non-catalyzed DNA. The reactivity of the two complexes was discussed in relation to other related artificial nucleases.     

Experimental and DFT studies on the DNA-binding trend and spectral properties of complexes [Ru(bpy)2L] (L = dmdpq, dpq, and dcdpq)

The trend in DNA-binding affinities and the spectral properties of a series of Ru(II) polypyridyl complexes, [Ru(bpy)₂(dmdpq)]²⁺ (1), [Ru(bpy)₂(dpq)]²⁺ (2), [Ru(bpy)₂(cndpq)]²⁺ (3) (bpy = 2,2′-bipyridine; dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline; dmdpq = di-methyl-dpq; dcdpq = di-cyano-dpq), have been experimentally and theoretically investigated. The DNA-binding constants K_b of the complexes were determined systematically with spectrophotometric titration. The density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were carried out for these complexes. The experimental results show that these complexes bind to DNA in intercalation mode, and the order of their intrinsic DNA-binding constants K_b is K_b(1) < K_b(2) ? K_b(3). The substituents on the intercalative ligands of the complexes play a very important role in the control of DNA-binding affinities of the complexes, in particular, the stronger electron-withdrawing substituent (-CN) on the intercalative ligand can greatly improve the DNA-binding property of the derivative complex. The trend in DNA-binding affinities as well as the spectral properties of metal-ligand charge-transition (¹MLCT) of this series of complexes can be reasonably explained by applying the DFT and TDDFT calculations and the frontier molecular orbital theory.     

Structural diversity and optical properties in the M-X-isonicotinic (M = Zn, Cd; X = Cl, Br, I) system: New zero-, one-, two- and three-dimensional inorganic-organic hybrids

Assembly of isonicotinic acid ligand (HL) with metal halide, five new hybrid complexes [CdI₂(C₅H₄NCOOH)(C₅H₄NHCOO)] · H₂O (1), Na_n[ZnCl₂(C₅H₄NCOO)]_n · 2nH₂O (2), [CdX(C₅H₄NCOO)]_n (X = Br (3), I (4)) and [Cd₃Cl₂(OH)₂(C₅H₄NCOO)₂]_n (5) were obtained, which display a variety of structural motifs, ranging from zero-dimensional to complicated three-dimensional networks. Complex 1 possesses an isolated unit MX₂ that is further connected into 3D networks through hydrogen bonding and π-π stacking interactions. Complex 2 is characterized by an infinite one-dimensional chain of zinc atoms bridged by L⁻ ligands. While complexes 3 and 4 possess X-bridging ^∞₁[CdX_2/2] inorganic chains connected by L⁻ ligands to form a 2D hybrid network structure. In the case of 5, the cadmium(II) cation is bridged by μ₃-Cl atom and μ₃-OH⁻ group to form a 2-D ^∞₂[Cd_6/2Cl_6/3(μ₃-OH)₂] inorganic layer which is further extended into 3-D framework by bridging L⁻ ligand via Cd-N and Cd-O bonds. The optical properties of 1, 4, and 5 in the solid state are investigated at room temperature and time-dependent DFT (TDDFT) calculation using the B3LYP functional has been performed on 1. The result indicated that the emission band of 1 is attributed to an admixture of MLCT (metal-to-ligand charge-transfer) and LLCT (ligand-to-ligand charge-transfer).     

Chemistry at the apical position of square-pyramidal copper(II) complexes: Synthesis, crystal structures, and magnetic properties of homopolynuclear complexes with azido bridges containing [Cu(AA)(BB)] moieties (AA = acetylacetonate; BB = 1,10-phenanthroline, bipy = 2,2′-bipyridine)

Three new homopolynuclear complexes with azido bridges have been obtained by using [Cu(AA)(BB)]⁺ building-blocks (AA = acetylacetonate; BB = 1,10-phenanthroline or 2,2′-bipyridine). The reaction between [Cu(acac)(phen)(H₂O)](ClO₄) and NaN₃ leads to a mixture of two compounds: a binuclear complex, [{Cu(acac)(phen)}₂(μ_1,3-N₃)](ClO₄) · 2H₂O (1), and a linear tetranuclear one, [{Cu(acac)(phen)(ClO₄)}₂{Cu(phen)(μ_1,1-N₃)₂}₂] (2). The reaction between [Cu(acac)(bipy)(H₂O)](ClO₄) and NaN₃ affords also a mixture of two compounds: [{Cu(acac)(bipy)}₂(μ_1,3-N₃)]₃(ClO₄)₃ · 3.75H₂O (3) and [Cu(acac)(bipy)(N₃)][Cu(acac)(bipy)(H₂O)](ClO₄) (4). The X-ray crystal structures of compounds 1-4 have been solved (for compound 4 the crystal structure was previously reported). In compounds 1 and 3, two {Cu(AA)(BB)} fragments are bridged by the azido anion in an end-to-end fashion. Two isomers, cis and trans with respect to azido bridge, were found in crystal 3. The structure of compound 2 consists of two Cu(II) central cations bridged by two μ_1,1-azido ligands, each of them being also connected to a {Cu(acac)(phen)} fragment through another μ_1,1-azido ligand. The cryomagnetic properties of the compounds 1 and 2 have been investigated and discussed. The magnetic behaviour of compound 1 shows the absence of any interactions between the metallic ions. In the tetranuclear complex 2, the magnetic interactions between the external and central copper(II) ions(J₁), and between the central metallic ions (J₂) were found ferromagnetic (J₁ = 0.36 cm⁻¹, J₂ = 7.20 cm⁻¹).     

Two new supermolecular structures of organic-inorganic hybrid compounds: [Zn(phen)(SO4)(H2O)2]n and [Cu(phen)(H2O)2] · SO4 (phen = 1,10-phenanthroline)

Two new organic-inorganic hybrid compounds [Zn(phen)(SO₄)(H₂O)₂]_n (1) and [Cu(phen)(H₂O)₂] · SO₄ (2) have been prepared by conventional aqueous solution synthesis and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. In compound 1, the sulfate group adopts bidentate mode to coordinate with two Zn(II) ions to form one-dimensional polymer. The one-dimensional polymers are further linked together via the intermolecular hydrogen-bonding and π-π stacking interactions to form a 3D supramolecular framework. Compound 2 is build up of discrete [Cu(phen)(H₂O]²⁺ cations and SO₄²⁻ anions to form a three-dimensional framework via hydrogen-bonding and π-π stacking interactions. Furthermore, the luminescent properties of both 1 and 2 were studied. The complexes 1 and 2 excited at 280 nm wavelength produced characteristic luminescence features, arising maybe due to the π-π transitions.     

Synthesis, structures, and magnetic properties of dicopper(II) and dinickel(II) complexes with a new bis(macrocycle), 7,7-(2-hydoxypropane-1,3-diyl)bis{3,7,11,17-tetraazabicyclo[11.3.1]- heptadeca-1(17),13,15-triene}

A new bis(macrocycle) ligand, 7,7^′-(2-hydoxypropane-1,3-diyl)-bis{3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene} (HL), and its dicopper(II) ([Cu₂(HL)Cl₂](NO₃)₂ · 4H₂O (4a), [Cu₂(HL)I₂]I₂ · H₂O (4b)) and dinickel(II) ([Ni₂(L)(OH₂)](ClO₄)₃ (5a), [Ni₂(L)(OH₂)]I₃ · 2H₂O (5b), [Ni₂(L)N₃](N₃)₂ · 7H₂O (5c)) complexes have been synthesized. The alkoxide bridged face-to-face structure of the dinickel(II) complex 5c has been revealed by X-ray crystallography, as well as the “half-opened clamshell” form of the bis(macrocyclic) dicopper(II) complex 4b. Variable temperature magnetic susceptibility studies have indicated that there exists intramolecular antiferromagnetic coupling (J=−33.8 cm⁻¹ (5a), −32.5 cm⁻¹ (5b), and −29.7 cm⁻¹ (5c)) between the two nickel(II) ions in the nickel(II) complexes.     

Synthesis, structures and DNA binding of ternary transition metal complexes M(II)L with the 2,2-bipyridylamine (L = p-HB, M = Co, Ni, Cu and Zn)

New ternary transition metal complexes of formulations [Co(bpa)(p-HB)₂](bpa = 2,2′-bipyridylamine, p-HB = p-hydroxybenzenecarboxylic acid) (1), [Ni(bpa)(p-HB)(H₂O)₂]⁺(NO₃)⁻ · H₂O (2), , [Cu(bpa)(p-HB)Cl] (4) and [Zn(bpa)(p-HB)₂]₂ · 0.5H₂O (5) are prepared, their structural features are characterized by crystal structural studies, and their DNA binding propensity has been evaluated by fluorescence method. The molecular structure of complex 1 shows the six coordinate octahedral geometry with one bpa and two p-HB ligands, complex 2 is the cationic complex and has the six coordinate octahedral structure with one bpa, one p-HB and two aqua ligands, complex 3 is also the cationic complex of octahedral coordination with two bpa and one p-HB ligands, complex 4 is five coordinate distorted square pyramidal with one bpa, one p-HB and chloride ligands and complex 5 has the distorted octahedral coordination with two p-HB and one bpa ligands. In all of the complexes, both bpa and p-HB act as the bidentate N and O-donor ligands, respectively. The intermolecular H-bond networks, together with π-π interaction in their solid state are also described. The complexes show the competitive inhibition of ethidium binding to DNA, and the DNA binding propensity can be reflected as the relative order: 3 > 2 > 1 > 5 > 4, in which the cationic charged Ni(II) complexes 2 and 3 show the most effective inhibition ability.     

Synthesis, structures and magnetic properties of oxamido-bridged trinuclear Cu-M-Cu macrocyclic complexes (M = Mn(II) and Co(II))

Two oxamido-bridged trinuclear complexes of formula {[(LCu)(EtOH)]₂Mn(EtOH)₂}(ClO₄)₂ (1) and {[(LCu)(EtOH)]₂Co(EtOH)₂}(ClO₄)₂ · 2H₂O (2) (H₂L = 2,3-dioxo-5,6:13,14-dichlorobenzo-7,12-diphenyl-1,4,8,11-tetraazacyclo-pentadeca-7,11-diene) have been synthesized and structurally characterized. The central ions of complexes 1-2 (Mn(II), Co(II)) are all bridged by macrocyclic oxamido groups. Their magnetic properties were studied by susceptibility versus temperature measurement, the best fitting of the experimental data led to J = −16.91 cm⁻¹ for 1 and J = −27.73 cm⁻¹ for 2.     

Three trinuclear Cu-M-Cu (M = Co, Ni and Zn) complexes including macrocyclic oxamido bridge: Synthesis, structures and magnetic properties

Based on the complex ligand (CuL H2L = 2,3-dioxo-5,6:15,16-dibenzo-1,4,8,13-tetraazacyclotetradeca-7,13-diene), which includes macrocyclic oxamido bridge, three trinuclear complexes were prepared. They are of the formula [(CuL)₂M(ClO₄)₂] (M = Co(1), Ni(2)) and [(CuL)₂Zn(CH₃OH)₂] · (ClO₄)₂ (3). The crystal structures of the three complexes have been determined and the M(II) of the three complexes all exist on the mirror plane. Complex 1 is the first Cu-Co complex bridged by oxamido. Their magnetic properties were studied by susceptibility versus temperature measurement, the best fitting of the experimental data led to J = −28.12 cm⁻¹ for 1, J = −42.88 cm⁻¹ for 2, and J = −2.13 cm⁻¹ for 3.     

The reactivity of NbX5 (X = F, Cl) with lactons, lactams, and the synthesis of the first nucleobase-containing niobium complex

NbX₅ (X = F, 1a; X = Cl, 1b) reacted with γ-butyrolactone (but), ε-caprolactam (cap), δ-valerolactam (val) in 1:1 M ratio in chlorinated solvent, affording either the neutral coordination adducts NbCl₅L (L = but, 2a; L = val, 2b) or the ionic ones [NbX₄L₂][NbX₆] (X = F, L = but, 3a; X = F, L = val, 3b; X = F, L = cap, 3c; X = Cl, L = cap, 3d). The reaction of 1a with equimolar amount of guanine (gua) in CH₃CN resulted in the formation of the complex [NbF₄(gua)₂][NbF₆], 3e. The addition of two equivalents of organic substrate to 1 gave selectively the compounds NbCl₅L₂ (L = but, 4a; L = val, 4b) or [NbF₄L₄][NbF₆] (L = but, 5a; L = val, 5b; L = cap, 5c). The 1:2 M reaction of 1b with ε-caprolactam proceeded with C-N bond activation and afforded the derivative , 6, in high yield.     

Synthesis and characterization of Fe(III)(3-CH3O-qsal)2PF6 · nH2O (n = 0, 2)

Compounds Fe^III(3-CH₃O-qsal)₂PF₆ · nH₂O (n = 0, 2) (1, 1 · 2H₂O) were synthesized and characterized: the structure of 1 and the magnetic properties of both compounds were determined. Compound 1 · 2H₂O presents properties characteristic of high-spin Fe(III), while 1 presents properties of low-spin Fe(III) with an onset of a gradual spin crossover at ca. 300 K.     

fac-/mer-[RuCl3(NO)(P-N)] (P-N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine): Synthesis, characterization and DFT calculations

Complex fac-[RuCl₃(NO)(P-N)] (1) was synthesized from the reaction of [RuCl₃(H₂O)₂(NO)] and the P-N ligand, o-[(N,N-dimethylamino)phenyl]diphenylphosphine) in refluxing methanol solution, while complex mer,trans-[RuCl₃(NO)(P-N)] (2) was obtained by photochemical isomerization of (1) in dichloromethane solution. The third possible isomer mer,cis-[RuCl₃(NO)(P-N)] (3) was never observed in direct synthesis as well as in photo- or thermal-isomerization reactions. When refluxing a methanol solution of complex (2) a thermally induced isomerization occurs and complex (1) is regenerated.The complexes were characterized by NMR (³¹P{¹H}, ¹⁵N{¹H} and ¹H), cyclic voltammetry, FTIR, UV-Vis, elemental analysis and X-ray diffraction structure determination. The ³¹P{¹H} NMR revealed the presence of singlet at 35.6 for (1) and 28.3 ppm for (2). The ¹H NMR spectrum for (1) presented two singlets for the methyl hydrogens at 3.81 and 3.13 ppm, while for (2) was observed only one singlet at 3.29 ppm. FTIR Ru-NO stretching in KBr pellets or CH₂Cl₂ solution presented 1866 and 1872 cm⁻¹ for (1) and 1841 and 1860 cm⁻¹ for (2). Electrochemical analysis revealed a irreversible reduction attributed to Ru^II-NO⁺ → Ru^II-NO⁰ at −0.81 V and −0.62 V, for (1) and (2), respectively; the process Ru^II → Ru^III, as expected, is only observed around 2.0 V, for both complexes.Studies were conducted using ¹⁵NO and both complexes were isolated with ¹⁵N-enriched NO. Upon irradiation, the complex fac-[RuCl₃(NO)(P-N)] (1) does not exchange ¹⁴NO by ¹⁵NO, while complex mer,trans-[RuCl₃(NO)(P-N)] (2) does. Complex mer,trans-[RuCl₃(¹⁵NO)(P-N)] (2′) was obtained by direct reaction of mer,trans-[RuCl₃(NO)(P-N)] (2) with ¹⁵NO and the complex fac-[RuCl₃(¹⁵NO)(P-N)] (1′) was obtained by thermal-isomerization of mer,trans-[RuCl₃(¹⁵NO)(P-N)] (2′).DFT calculation on isomer energies, electronic spectra and electronic configuration were done. For complex (1) the HOMO orbital is essentially Ru (46.6%) and Cl (42.5%), for (2) Ru (57.4%) and Cl (39.0%) while LUMO orbital for (1) is based on NO (52.9%) and is less extent on Ru (38.4%), for (2) NO (58.2%) and Ru (31.5%).     

TTF charge transfer salts containing cyanometallate anions [M(phen)(CN)4] (M = Cr or Fe; phen = 1,10-phenanthroline)

Two new charge transfer salts of TTF with the counter anions [M(phen)(CN)₄]⁻ (phen = 1,10-phenanthroline, M = Cr (I) and Fe (II)) are described. The structures consist of alternating stacks of dimerised TTF⁺ cations and [M(phen)(CN)₄]⁻ anions and they are linked together by many short S?S contacts and hydrogen bonds. Within the organic stack, two dimerised TTF⁺ cations are arranged in a slipped face-to-face mode with short intra-dimer and long inter-dimer S?S distances. Strong antiferromagnetic exchange was found in the TTF⁺ dimers. Conductivity measurements show that compound I is a semiconductor.     

Palladium(II), platinum(II), ruthenium(II) and mercury(II) complexes of potentially tridentate Schiff base ligands of (E, N, O) type (E = S, Se, Te): Synthesis, crystal structures and applications in Heck and Suzuki coupling reactions

Schiff bases of 2-hydroxybenzophenone (HBP) (C₆H₅)(2-HOC₆H₄)CN(CH₂)_nEAr (L1/L2: E = S, Ar = Ph, n = 2/3; L3/L4: E = Se, Ar = Ph, n = 2/3; L5/L6: E = Te, Ar = 4-MeOC₆H₄, n = 2/3) and their complexes [PdCl(L-H)] (L = L1−L6; 1, 2, 3, 5, 7, 11), [PtCl(L3-H/L5-H)] (4/8), [PtCl₂(L4/L6)₂] (6/12), [(p-cymene)RuCl(L5/L6)]Cl (9/13) and [HgBr₂(L5/L6)₂] (10/14) have been synthesized and characterized by proton, carbon-13, selenium-77 and tellurium-125 NMR, IR and mass spectra. Single crystal structures of L1, 1, 3, 4, 5 and 7 were solved. The Pd-E bond distances (Å): 2.2563(6) (E = S), 2.3575(6)−2.392(2) (E = Se); 2.5117(5)−2.5198(5) (E = Te) are near the lower end of the bond length range known for them. The Pt-Se bond length, 2.3470(8) Å, is also closer to the short values reported so far. The Heck and Suzuki reaction were carried out using complexes 1, 3, 5 and 7 as catalysts under aerobic condition. The percentage yields for trans product in Heck reaction were found upto 85%.     

Transition metal halide salts of 8-methylquinolinium: Synthesis and structures of (8-methylquinolinium)2 MX4·nH2O (M = Cu, Co, Zn; X = Cl, Br; n = 0, 1)

The reactions of metal(II) chlorides and bromides with 8-methylquinoline (8-mequin) in neutral and acidic solutions were investigated. The reaction with ZnCl₂, ZnBr₂, CoCl₂, CoBr₂, CuCl₂ or CuBr₂ with the appropriate HX in water or aqueous ethanol gave complexes of the formula (8-mequin)₂MX₄ (1, M = Cu, X = Cl; 2, M = Cu, X = Br; 3, M = Co, X = Cl; 4, M = Co, X = Br) or (8-mequin)₂ZnX₄·nH₂O (5, X = Cl, n = 0; 6, X = Br, n = 0; 7, X = Cl, n = 1; 8, X = Br, n = 1). Crystals of 1, 2 and 4-8 suitable for single crystal X-ray diffraction were obtained and the structures reported. Compounds 1 and 2 crystallize in the monoclinic space group C2/c, while 4-8 crystallize in the triclinic space group, . Variable temperature magnetic susceptibility data indicate very weak interactions for the copper compounds 1 and 2, while the magnetic behavior of 3 and 4 is dominated by single ion anisotropy, with weaker antiferromagnetic interactions.     

Dioxouranium complexes as ligand. Synthesis and characterization of sandwich-type polyoxometalates [X2W18(UO2)2{(H2O)3M}2O68] (X = As and P) (M = Co, Cu, Mn, Ni and Zn)

The title complexes are synthesized by the reaction of an unusual ligand of [K₂P₂W₁₈(UO₂)₂O₆₈]¹²⁻ (1) and [KAs₂W₁₈(UO₂)₂O₆₈]¹³⁻ (2) with divalent metal ions of Co^II, Cu^II, Mn^II, Ni^II and Zn^II in 1:2 mole ratio and are characterized by elemental analysis, IR, ³¹P NMR, UV-Vis spectroscopy, TGA, and single crystal structure analysis. Crystals of [P₂W₁₈(UO₂)₂{(H₂O)₃Co}₂O₆₈]¹⁰⁻ (1a) and [As₂W₁₈(UO₂)₂{(H₂O)₃Cu}₂O₆₈]¹⁰⁻ (2b) are orthorhombic space group Cmca. Both 1a and 2b have structures in which two [M(H₂O)₃] (M = Co^II, Cu^II) and two UO₂ groups are sandwiched between two symmetry equivalent (XW₉) (X = P, As) units in a virtual C_i symmetry. In solution, 1a and [P₂W₁₈(UO₂)₂{(H₂O)₃Zn}₂O₆₈]¹⁰⁻ (1d) give two-line P NMR spectra that are consistent with a C_s symmetry structures so, are not consistent with the solid-state structures. The sodium salts of them give one-line P NMR spectra and are consistent with the C_i symmetry of solid-state structures. The uranium atoms have pentagonal-bipyramidal coordination, achieved by three equatorial bonds to the one XW₉ and two bonds to the other. The M atoms have octahedral or square pyramidal coordination, but only one bond to the one XW₉ and one bond to the other.     

Syntheses, crystal structures and properties of [K(2,2,2-crypt)]3K(HP7)2 · en, [K(18-crown-6)]2HP7 and [K(db18-crown-6)]2HP7 · toluene

The polyphosphide anions in ethylenediamine/2,2,2-crypt, ethylenediamine/18-crown-6 and ethylenediamine/db18-crown-6 solutions are isolated as K[K(2,2,2-crypt)]₃(HP₇)₂ · en (1), [K(18-crown-6)]₂HP₇ (2) and [K(db18-crown-6)]₂HP₇ · toluene (3). The mono-protonation of the P₇ cluster is observed in all three compounds. The (HP₇)²⁻ units are stabilized by naked potassium in 1 and complexing potassium in 2 and 3. The significant C-H?P hydrogen bonding interaction is observed in 3, which is responsible for the 3-D supramolecular structure. The 3-D supramolecular structure is also contributed by the η²-interaction between K⁺ and the phenyl. The ³¹P and ¹H NMR spectra of 1-3 indicate that the polyphosphide anions are very fluxional in solution.