Synthesis, characterization and bioactivity of two novel trinuclear Cu(II)/Ni(II) complexes with pentadentate ligand N-2-methyl-acryloyl-salicylhydrazide

Two new trinuclear complexes, Cu₃L₂(py)₂ (1) and Ni₃L₂(py)₄ (2), have been synthesized and characterized, where L³⁻ is N-2-methyl-acryloyl-salicylhydrazidate. Central metal ion and two terminal metal ions in the two complexes are combined by two bridging deprotonated L³⁻ ligands, forming a bent trinuclear structure unit with an M-N-N-M-N-N-M core. The bent angles in complexes 1 and 2 are 167.6(1)° and 75.4(1)°, respectively. Three nickel ions in compound 2 exhibit alternating square-planar and octahedral geometries, while three copper ions in compound 1 follow square-planar mode. The studies in solution integrity and stability of compounds 1 and 2 show they are soluble and stable in DMF. UV-Vis titrations demonstrate compound 1 is stable in DMF even in the presence of excess metal ions. Antibacterial screening data indicate the two compounds all have stronger antimicrobial activities against the tested microorganisms than ligand. The trinuclear copper compound 1 is more active than monocopper compounds in the previous study, and the trinuclear nickel compound 2 is less active than tetranuclear nickel compound in the previous study.     

Coordination polymers of unsymmetrical angular ligand 3-pyridin-4-ylbenzoate acid: Syntheses, structural diversity and properties

Six new 1-3D coordination polymers of an unsymmetrical angular ligand 3-pyridin-4-ylbenzoate (L), namely, [Ni(L)₂(C₂H₆O₂)]_n (1), [Cd(L)₂(H₂O)₂]_n·4H₂O (2), [Zn₂(OH)(L)₃]_n (3), [Fe₂(OH)(L)₃]_n (4), [Ni(L)₂(H₂O)]_n (5) and [Cd(L)₂(H₂O)]_n (6) were hydro(solvo)thermally synthesized. They have abounding structure chemistry ranging from one-dimensional ribbons (1 and 2), and two-dimensional novel helical double-layered frameworks (3 and 4) to three-dimensional CdSO₄-topological porous interpenetrating architectures with hydrophilic and hydrophobic channels regularly arraying (5 and 6). The labile conformations and coordination modes of ligand L, which were finely tuned by reaction conditions, perhaps play the key role in the construction of various architectures. Very interestingly, the slight difference in solvent system or temperature resulted in the distinct architectures of nickel(II) complexes 1 and 5 or cadmium(II) complexes 2 and 6. As expected, the unsymmetrical ligand L has a trend to construct metal-organic helixes as observed in 3 and 4. Thermogravimetric analysis of 5 shows the main framework retains stability until a higher temperature 379 °C. The 3D microporous network of 5 can slightly absorb for N₂ and Ar. Compounds 2, 3 and 6 emit ligand-centered photoluminescence but with obviously different intensities owing to the structural diversities and coordinating water molecules.     

Mn(II) coordination architectures with mixed ligands of 3-(2-pyridyl)pyrazole and carboxylic acids bearing different secondary coordination donors and pendant skeletons

In our efforts to investigate the factors that affect the formation of coordination architectures, such as secondary coordination donors and pendant skeletons of the carboxylic acid ligands, as well as H-bonding and other weak interactions, two kinds of ligands: (a) 3-(2-pyridyl)pyrazole (L¹) with a non-coordinated N atom as a H-bonding donor, a 2,2′-bipyridyl-like chelating ligand, and (b) four carboxylic ligands with different secondary coordination donors and/or pendant skeletons, 1,4-benzenedicarboxylic acid (H₂L²), 4-sulfobenzoic acid (H₂L³), quinoline-4-carboxylic acid (HL⁴) and fumaric acid (H₂L⁵), have been selected to react with Mn(II) salts, and five new complexes, [Mn(L¹)₂(SO₄)]₂ (1), [Mn(L¹)₂(L²)]_∞ (2), [Mn(L¹)(HL³)₂]_∞ (3), Mn(L¹)₂(L⁴)₂ (4), and [Mn(L¹)₂(L⁵)]_∞ (5), have been obtained and structurally characterized. The structural differences of 1-5 can be attributed to the introduction of the different carboxylic acid ligands (H₂L², H₂L³, HL⁴, and H₂L⁵) with different secondary coordination donors and pendant skeletons, respectively. This result also reveals that the typical H-bonding (i.e. N-H?O and O-H?O) and some other intra- or inter-molecular weak interactions, such as C-H?O weak H-bonding and π?π interactions, often play important roles in the formation of supramolecular aggregates, especially in the aspect of linking the multi-nuclear discrete subunits or low-dimensional entities into high-dimensional supramolecular networks.     

Preparation of [meso-tetraphenylchlorophinato]nickel(II) by stepwise deformylation of [meso-tetraphenyl-2,3-diformyl-secochlorinato]nickel(II): conformational consequences of breaking the structural integrity of nickel porphyrins

The stepwise, Wilkinson’s catalyst-induced decarbonylation of [meso-tetraphenyl-2,3-diformylsecochlorinato]Ni(II) (4) to produce the monoformylated pigment [meso-tetraphenyl-2-formylsecochlorinato] (5) and [meso-tetraphenylchlorophinato]Ni(II) (6) is described. Thus, we have shown how to degrade one pyrrolic unit of the starting material, [meso-tetraphenylporphyrinato]Ni(II) (2) in three steps to an aldimine linkage. The conformational changes of the porphyrinic macrocycle during the course of this degradation, as determined by comparison of the X-ray crystal structures of the compounds, are discussed. A comparative study delineates the UV-Vis spectroscopical consequences. In addition, the chemical reactivity of [meso-tetraphenylchlorophinato]Ni(II) (6) suggests the existence of an azepine-derived pyrrole-modified porphyrins (11, 12).     

Structure–activity relationships of new 4-hydroxy bis-coumarins as radical scavengers and chain-breaking antioxidants

The main antioxidant properties of five new 4-hydroxy-bis-coumarins during bulk lipid autoxidation at 80 °C and 0.1 mM and 1.0 mM concentrations were studied and compared with 4-hydroxy-2H-chromen-2-one (1). These compounds are: 3,3′-((3,4-dihydroxy-phenyl) methylene) bis (4-hydroxy-2H-chromen-2-one) (2), 3,3′-((3,4-dimethoxyphenyl) methylene) bis (4-hydroxy-2H-chromen-2-one) (3), 3,3′-((4-hydroxy-3,5-dimethoxy-phenyl) methylene) bis(4-hydroxy-2H-chromen-2-one) (4) 3,3′-((3,4,5- trimethoxyphenyl) methylene) bis (4-hydroxy-2H-chromen-2-one) (5) 3,3′-((4-hydroxy-3-methoxy-5-nitrophenyl) methylene) bis (4-hydroxy-2H-chromen-2-one) (6), It was found that compound 2 with a catecholic structure in the aromatic nucleus showed the strongest antioxidant activity. Compound 4 showed a moderate antioxidant activity, and all the other compounds didn't show any capacity as chain-breaking antioxidants. Both 4-hydroxy-bis-coumarins (2 and 4) demonstrated also stronger radical scavenging activity towards DPPH radical by using TLC DPPH rapid test, than compound 1. The other compounds (3, 5, 6) didn't show any capacity as radical scavengers. The structure–activity relationship was discussed on the base of comparable kinetic analysis of studied 4-hydroxy-bis-coumarins with the known and standard antioxidants as α-tocopherol (TOH), caffeic acid (CA), sinapic acid (SA), ferulic acid (FA), and p-coumaric acid (p-CumA). In order to study the possible synergism between two phenolic antioxidants, the antioxidant efficiency and reactivity of two equimolar binary mixtures of coumarins and TOH (2 + TOH and 4 + TOH) and of corresponding cinnamic acid with TOH (CA + TOH and SA + TOH) were also tested and compared. The oxidation stability of the lipid substrate in presence of binary mixtures CA + TOH, SA + TOH and 2 + TOH appeared to be higher than that of the individual antioxidants. However, no synergism was obtained for all tested binary mixtures.     

Synthesis, structure and antitumor activity of [RhCl3(N-N)(DMSO)] polypyridyl complexes

The [RhCl₃(N-N)(DMSO)] complexes, the N-N being 2,2′-bipyridine (1), 1,10-phenanthroline (2), 4,7-diphenyl-1,10-phenanthroline (3), 4,4′-dimethyl-2,2′-bipyridine (4) and 1,10-phenanthroline-5,6-dione (5), have been synthesized and characterized with spectroscopic methods. The compounds 2-5 adopt mer- and complex 1fac-structure. The molecular and electronic structure studies of mer- and fac-complexes with bpy and phen ligands at the DFT B3LYP level with 3-21G^∗∗ basis set showed that mer-isomers are more stable. The cytostatic activity of the [RhCl₃(N-N)(DMSO)] complexes against Caco-2 and A549 tumor cells have been studied. Their antibacterial activity have also been investigated. It has been found that the very promising biological activity show complexes 2, 3 and 4.     

Pyrinodemins E and F, new 3-alkylpyridine alkaloids from sponge Amphimedon sp

Two new 3-alkylpyridine alkaloids, pyrinodemins E (1) and F (2), were isolated from an Okinawan marine sponge Amphimedon sp. and the structures of 1 and 2 were elucidated on the basis of spectroscopic data. Pyrinodemins E (1) and F (2) were novel 3-alkylpyridine alkaloids possessing a 4-(methoxyamino)piperidinone moiety and an indol-3-glyoxylamide moiety, respectively. Pyrinodemin E (1) showed cytotoxicity against P388 and L1210 murine leukemia cells.     

Acyl-CoA binding domain containing 3 (ACBD3) recruits the protein phosphatase PPM1L to ER-Golgi membrane contact sites

The metal-dependent protein phosphatase family (PPM) governs a number of signaling pathways. PPM1L, originally identified as a negative regulator of stress-activated protein kinase signaling, was recently shown to be involved in the regulation of ceramide trafficking at ER-Golgi membrane contact sites. Here, we identified acyl-CoA binding domain containing 3 (ACBD3) as an interacting partner of PPM1L. We showed that this association, which recruits PPM1L to ER-Golgi membrane contact sites, is mediated by a GOLD (Golgi dynamics) domain in ACBD3. These results suggested that ACBD3 plays a pivotal role in ceramide transport regulation at the ER-Golgi interface.

Structured summary of protein interactions

ACBD3 and PPM1Lcolocalize by fluorescence microscopy (View interaction)FYCO1physically interacts with PPM1L by pull down (View interaction)SEC14L2physically interacts with PPM1L by pull down (View interaction)ACBD3physically interacts with PPM1L by pull down (View interaction)SEC14L1physically interacts with PPM1L by pull down (View interaction)PPM1Lphysically interacts with ACBD3 by two hybrid (View interaction)     

Discovery of novel ureas and thioureas of 3-decladinosyl-3-hydroxy 15-membered azalides active against efflux-mediated resistant Streptococcus pneumoniae

A series of novel ureas and thioureas of 3-decladinosyl-3-hydroxy 15-membered azalides, were discovered, structurally characterized and biologically evaluated. They have shown good antibacterial activity against selected Gram-positive and Gram-negative bacterial strains. These include N″ substituted 9a-(N′-carbamoyl-γ-aminopropyl)- (6a,c), 9a-(N′-thiocarbamoyl-γ-aminopropyl)- (7a,e), 9a-[N′-(β-cyanoethyl)-N′-(carbamoyl-γ-aminopropyl)]- (9a-c, 9g) 9a-[N′-(β-cyanoethyl)-N′-(thiocarbamoyl-γ-aminopropyl)]-derivatives (10d-f) of 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerythronolide A (3).Among the synthesized compounds thiourea 7a and urea 9b have shown substantially improved activity comparable to azithromycin (1) and significantly better activity than the 3-decladinosyl-azithromycin (2) and the parent 3-cladinosyl analogues against efflux-mediated resistant S. pneumoniae.     

Synthesis, characterization, crystal structures and photophysical properties of copper(I) complexes containing 1,1′-bis(diphenylphosphino)ferrocene (B-dppf) in doubly-bridged mode

Five copper(I) complexes having general formula [Cu₂(μ-X)₂(κ²-P,P-B-dppf)₂] (X = Cl(1), Br(2), I(3), CN(4), and SCN(5)) were prepared starting with CuX and B-dppf in 1:1 molar ratio in DCM-MeOH (50:50 V/V) at room temperature. The complexes have been characterized by elemental analyses, IR, ¹H NMR, ³¹P NMR and electronic spectral studies. Molecular structures for 1, 2 and 4 were determined crystallographically. Complexes 1, 2 and 4 exist as centrosymmetric dimers in which the two copper atoms are bonded to two bridging B-dppf ligands and two bridging (pseudo-)halide groups in a μ-η¹ bonding mode to generate nearly planar Cu₂(μ-η¹-X)₂ framework. Both bridging B-dppf ligands are arranged in antiperiplanar staggered conformation in 1 and 2 (mean value 56.40-56.76°), and twisted from the eclipsed conformation (mean value 78.19°) in 4. The Φ angle value in 4 is relatively larger as compared to 1 and 2. This seems to indicate that the molecular core [Cu₂(μ-η¹-X)₂] in 4 is a sterically demanding system that forces the B-dppf ligand to adopt a relatively strained conformation in comparison to less strained system in 1 and 2. All the complexes exhibit moderately strong luminescence properties in the solution state at ambient temperature.     

Cation control of dimensionality in isothiocyanate coordination polymers constructed from conformationally flexible 3,3′-bipyridine tethers

Two isothiocyanate coordination polymers constructed from the conformationally flexible tethering ligand 3,3′-bipyridine (3,3′-bpy) and divalent metal cations have been prepared and characterized via single crystal X-ray diffraction, infrared spectroscopy and elemental analysis. [Co(NCS)₂(3,3′-bpy)₂] (1), wherein the isothiocyanate ligands are coordinated in a trans fashion, manifests stacked two-dimensional (2-D) rhomboid grid layered motifs. In contrast, [Ni(NCS)₂(3,3′-bpy)₂] (2) possesses a doubly interpenetrated adamantoid three-dimensional (3-D) network despite the presence of trans isothiocyanate ligands. Thus, a metal cation-based control of coordination polymer dimensionality has been revealed in this system, reflective of different donor dispositions allowed by the conformational flexibility of the exobidentate 3,3′-bpy ligand. The 3-D framework of 2 decomposes at a temperature ∼40 °C higher than the 2-D network of 1.     

Spectroscopic characterization of mononuclear, binuclear, and insoluble polynuclear oxovanadium(IV)-Schiff base complexes and their oxidation catalysis

The objective was to prepare mononuclear, binuclear, and insoluble polynuclear oxovanadium(IV)-Schiff base complexes and to use them for sulfoxidation and epoxidation of organic substrates. [VO(salen)] (complex 1) with tetradentate salen(salicylideneethylenediamine) being coordinated in the equatorial plane of oxovanadium(IV), [VO(salap)] (complex 2), and [(VO)₂(sal₂-dhdabp)] (complex 3) with tridentate salap(salicylideneorthoaminophenol) and sal₂-dhdabp(salicylidene-3,3^′-dihydroxy-4,4^′-diaminobiphenyl) being bound, respectively, in the equatorial plane, of which polynuclear complexes were constituted as monomer units, were prepared and spectroscopically characterized. A sulfide and olefins were oxidized by use of complexes 1 and 2 (mononuclear), complex 3 (binuclear), and the polynuclear complexes (poly-1 and poly-3) synthesized with 1 and 3, respectively. The reaction rates for poly-1 and -3 were a little lower than those of the corresponding 1 and 3. On oxidation of sulfides, poly-3 exhibited lowering of activity by about 15% in three cycles, while poly-1 showed significant lose of activity with each use. Poly-3 was efficient for the oxidation of the olefins only in the first cycle. It was suggested that the loss of activity depends not only on the coordination geometry of the oxovanadium complex, but also on the kind of the substrate.     

A novel tetranuclear hydrogenphosphate-bridged Cu(II) cluster. Synthesis, structure, spectroscopy and magnetism of [Cu4(dpyam)4(μ4,η-HPO4)2(μ-X)2]X2(H2O)6 (X = Cl, Br)

Two novel tetranuclear compounds with an unprecedented mode of a hydrogenphosphato bridge, [Cu₄(dpyam)₄(μ₄,η³-HPO₄)₂(μ-X)₂]²⁺ (in which dpyam = di-2-pyridylamine and X = Cl (1), Br (2)) have been synthesised and characterised structurally and magnetically. The Cu(II) ions in the structures each display a square-pyramidal geometry, with two tridentate hydrogenphosphato groups bridging four copper atoms in a μ₄,η³ coordination mode which is rarely found in hydrogenphosphate metal compounds. Each (different) pair of Cu(II) ions is additionally bridged by halide ions, with relatively long Cu-X distances (2.551(3)-2.604(3) Å for 1 and 2.707(1)-2.766(2) Å for 2) and subsequently also a small Cu-X-Cu angle (65.7(1)° and 65.1(1)° for 1 and 61.6(1)° and 62.4(1) for 2) and a large Cu-X-Cu angle (95.5(1)° and 96.5(1)° for 1 and 91.1(1)° and 92.6(1)° for 2). Cu?Cu distances in the tetranuclear units varies from 2.802(3) to 5.232(3) Å for 1 and from 2.834(1) to5.233(1) Å in 2. The lattice structures are stabilised by extensive intermolecular hydrogen bonds. The magnetic susceptibility measurements down to 5 K revealed a weak ferromagnetic interaction between the outer pairs of Cu(II) ions which vary from 22 to 46 cm⁻¹ in 1 and 12 to 33 cm⁻¹ in 2 and a moderately strong antiferromagnetic interaction between the inner Cu(II) ions of −79 cm⁻¹ in 1 and −83 cm⁻¹ in 2, via the Cu-O-P-O-Cu pathway.     

Synthesis and characterization of cationic rhodium(I) dicarbonyl complexes

Treatment of Rh(acac)(CO)₂ (acac = acetoacetonate) with perchloric acid followed by addition of an α-diimine (α-diimine = 1,4-bis(Ar)-2,3-dimethyl-1,4-diaza-1,3-butadiene, Ar = 3,5-dimethylphenyl, 1; 3,5-di-tert-butylphenyl, 2; and 3,4,5-trimethoxyphenyl, 3; phenyl, 4; and 4-chlorophenyl, 5) generates a series of complexes of the type [Rh(α-diimine)(CO)₂][ClO₄] 6-10 with varying electronic properties of the supporting diimine ligand. X-ray crystal structures have been determined for the α-diimine ligands 1-5, and complexes 6, 8, and 10.     

The palladium complexes of a C3-bridged di(benzimidazol-2-ylidene) ligand via cleavage of a dibenzotetraazafulvalene

Reduction of the N1, N1′-C₃-bridged di(benzimidazol-2-thione) (5) with a sodium/potassium alloy leads to the N1, N1′-C₃-bridged dibenzotetraazafulvalene (6). One equivalent of 6 reacts with palladium diiodide to give the dicarbene complex 1,3-(2,2-dimethylpropane)-N1,N1′-bis(N3-ethylbenzimidazol-2-ylidene)palladium diiodide (7). The X-ray crystal structure analysis of 7 reveals a slightly distorted square-planar coordination environment for the palladium center and a C_carbene-Pd-C_carbene angle of 85.0(15)°. The carbene planes are oriented almost perpendicular (82.7° and 79.3°) to the PdI₂C₂ plane.     

Glycosylation of lysine-containing pentapeptides by glucuronic acid: new insights into the Maillard reaction

The formation of glycosylation products in model systems consisting of d-glucuronic acid (GlcA) and lysine-containing peptides, such as Lys-Gly-Gly-Phe-Leu (1), Gly-Lys-Gly-Phe-Leu (4) and Ac-Gly-Lys-Gly-Phe-Leu (6), was examined to evaluate the site specificity as well as the extent and nature of the modification. Peptides were reacted with GlcA either in solution or under dry-heating conditions. From the incubations performed in solution (MeOH), the corresponding (1-deoxy-d-fructofuranos-1-yluronic acid)-peptide derivatives (Amadori compounds) were isolated. Whereas reaction of 1 resulted in the formation of mono-glycosylated Amadori compound 2 with the sugar moiety attached to the N^ε-amino group of the Lys residue and its di-glycosylated analogue 3, exposure of 4 to GlcA afforded only di-glycosylated peptide 5. From the incubation of GlcA with Ac-Gly-Lys-Gly-Phe-Leu (6) performed under mild dry-heating conditions (50 °C) in an environment of 75% relative humidity, besides Amadori compound 7, two new Maillard reaction products were isolated that contained 3-hydroxypyridinium (8) and 3-hydroxy-picolinic acid moiety (9). The mechanism for the formation of pyridinium products is discussed.     

Rh(I) complexes containing tris(pyrazolyl)amine and bis(pyrazolyl)amine ligands: synthesis and NMR studies

The tris(pyrazolyl)amine ligands: tris[2-(1-pyrazolyl)methyl]amine (tpma), tris [3,5-dimethyl-1-pyrazolyl)methyl]amine (tdma), tris[2-(1-pyrazolyl)ethyl]amine (tpea), tris[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (tdea) and bis(pyrazolyl)amine ligands: bis[2-(1-pyrazolyl)ethyl]amine (bpea) and bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (bdea) react with [RhCl(cod)]₂ in presence of NaBF₄ (tpma, tdma and bdea) or AgBF₄ (tpea, tdea and bpea) to lead to [Rh(cod)L] (BF₄) (L=tpma (1), tdma (2), bdea (3), tpea (4), tdea (5) and bpea (6)). These complexes have been characterised by elemental analyses, conductivity, IR, ¹H and ¹³C NMR spectroscopy and liquid mass (with electrospray) spectrometry. The ¹H NMR spectra of 1, 2 show the presence of two isomers in solution in a 3:1 ratio (coordination κ² or κ³ type) in a thermodynamic equilibrium. The steric bulk of cyclo-octa-1,5-diene causes it to prefer the κ² mode of bonding as majority. Similar to previous published results, complexes 4 and 5 exist in a sole form in solution (probably κ² isomer). Finally, the complexes 3 and 6 are fluxional. A NMR study shows that this fluxional process is not frozen at 183 K.     

Phytotoxic constituents from Nimbya alternantherae

A phytotoxic compound identified as 6-(3,3-dimethylallyloxy)-4-methoxy-5-methylphthalide (1), was isolated from the phytopathogenic fungus Nimbya alternantherae, cultivated on solid media. Catalytic hydrogenation of 1 resulted in the quantitative formation of second compound (2). Both compounds (1, 2) act by inhibiting the ATP synthesis in spinach thylakoids. A detailed investigation on the mechanism of action indicates that compound 1 acts as a Hill reaction inhibitor and uncoupler of photosynthesis.     

Synthesis and characterization of new AMTTO-imine-ligands and their silver(I) complexes: crystal structures of TAMTTO, [Ag2(TAMMTO)4](NO3)2 · 4MeOH, [Ag(TAMTTO)(PPh3)2]NO3 · 1.5THF, [Ag(FAMTTO)(PPh3)2]NO3

Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treatment of 2 with AgNO₃ gave the complex [Ag₂(TAMMTO)₄](NO₃)₂ · 4MeOH (4) and of 2 and 3 with [Ag(PPh₃)₂]NO₃ gave the complexes [Ag(TAMTTO)(PPh₃)₂]NO₃ · 1.5THF (5) and [Ag(FAMTTO)(PPh₃)₂]NO₃ (6), respectively. All the compounds have been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by ³¹P NMR spectroscopy. Crystal data for 2 at −80 °C: monoclinic, space group C2/c, a=2319.6(2), b=609.8(1), c=1673.6(2) pm, β=106.14(1)°, Z=8, R₁=0.0523; for 4 at −80 °C: triclinic, space group , a=877.6(1), b=1085.2(1), c=1557.7(2) pm, α=77.14(1)°, β=80.87(1)°, γ=78.18(1)°, Z=1, R₁=0.0407; for 5 at 20 °C: triclinic, space group , a=1151.1(2), b=1225.1(2), c=1887.4(3) pm, α=78.04(1)°, β=86.20(1)°, γ=76.03(1)°, Z=2, R₁=0.0662; for 6 at −80 °C: triclinic, space group , a=1189.7(2), b=1387.8(2), c=1410.9(2) pm, α=94.74(2)°, β=95.12(2)°, γ=112.41(2)°, Z=2, R₁=0.0511.     

Sn-S and Ru-Ru bonds cleavage reactions between [Ph3SnS(CH2)3SSnPh3] and Ru3(CO)12: X-ray crystal structures of [Ph3SnS(CH2)3SSnPh3] and trans-[Ru(CO)4(SnPh3)2]

The organotin complex [Ph₃SnS(CH₂)₃SSnPh₃] (1) was synthesized by PdCl₂ catalyzed reaction between Ph₃SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru₃(CO)₁₂ in refluxing THF affords the mononuclear complex trans-[Ru(CO)₄(SnPh₃)₂] (2) and the dinuclear complex [Ru₂(CO)₆(μ-κ²-SCH₂CH₂CH₂S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh₃ (pymS = pyrimidine-2-thiolate) with Ru₃(CO)₁₂ at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.