Hexa- and triosmium carbonyl clusters bearing bridging dppm and capping sulfido ligands

Treatment of [Os₃(CO)₇(μ₃-S)₂(μ-dppm)] (1) with Me₃NO in toluene at 80 °C affords the trinuclear cluster [Os₃(CO)₆(μ₃-S)₂(NMe₃)(μ-dppm)] (2) and the hexanuclear cluster [Os₆(CO)₁₂(μ₃-S)₄(μ-dppm)₂] (3) in 30% and 51% yields, respectively. The reaction of 1 with [Os₃(CO)₁₀(MeCN)₂] in refluxing benzene at 80 °C gives the hexanuclear cluster [Os₆(CO)₁₄(μ₃-S)₂(μ-dppm)] (4) in 15% yield. Compound 2 reacts with CO, PPh₃ and P(OMe)₃ at room temperature to give 1, [Os₃(CO)₆(μ₃-S)₂(μ-dppm)(PPh₃)] (5) and [Os₃(CO)₆(μ₃-S)₂(μ-dppm){P(OMe)₃}] (6), respectively; in high yields indicating that the NMe₃ ligand is weakly bound. Compound 1 reacts with PPh₃ in presence of Me₃NO to afford 5, 2 and 3 in 53%, 6% and 18% yields, respectively, whereas with P(OMe)₃1 gives only 6 in 84% yield. Compound 3 reacts with CO at 98 °C to regenerate 1 by the cleavage of the three unsupported osmium-osmium bonds. The molecular structures of 4 and 6 have been unambiguously determined by single crystal X-ray diffraction studies. The hexanuclear compound 3 appears to be a64-electron butterfly core with four triply bridging sulfido ligands and two bridging dppm ligands based on the spectroscopic and analytical data. The metal core of 4 can be described as a central tetrahedral array capped on two faces with two additional osmium atoms. The triply bridging sulfido ligands face cap the two tetrahedral arrays formed by metal capping of the two faces of the central tetrahedron. The dppm ligand bridges one edge of one of the external tetrahedral arrays. Compounds 5 and 6 are formed by the displacement of equatorial carbonyl group of 1 by a PPh₃ and P(OMe)₃ ligand respectively and their structures are comparable to that of 1.     

Synthesis, structures and reactivity of triosmium clusters containing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands

Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os₃(CO)₁₂] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me₃NO in moderate yields. Compounds [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os₃(CO)₉(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh₃; 6, L′ = P(OMe)₃; 7, L′ = ^tBuNC; 8, L′ = C₅H₅N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms.     

Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation

The reaction of (Ph₃P)₃RuCl₂ with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh₃)₂Cl₂Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C₃-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh₃)₂ClRu(μ-Cl)₃(PPh₃)₂RuCCCPh₂ complex (5). The reaction of (Ph₃P)₃₋₄RuCl₂ with 1,1-diphenyl-2-propyn-1-ol in CH₂Cl₂ or C₂H₄Cl₂ under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh₃)₂Cl₃RuC-CHCPh₂ carbyne complex (7), an HCl adduct of previously elusive (PPh₃)₂Cl₂RuCCCPh₂ complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C₃-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H₂O) to give hexacoordinate (PPh₃)₂Cl₂(ROH)RuCCCPh₂ (R = H, CH₃, C₂H₅) complexes (9)-(11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-(N,N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh₃)₂Cl₂(DMAP)RuCCCPh₂complex (12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh₃)₂Cl₂RuC(OCH₃)-CHCPh₂ (14) and (PPh₃)₂Cl₂RuC(OAc)-CHCPh₂ (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9-11, 14, and 15 were solved via X-ray crystallography.     

Heterometallic iron carbonyl chalcogenide clusters containing ruthenium,rhenium, manganese,and molybdenum

The reactions of Fe₂Se₂(CO)₆ (1b) with Ru(CO)₄(C₂H₄), Mn₂(CO)₁₀, or Np"Re(CO)₂THF gave the known cluster Fe₂RuSe₂(CO)₉ (4b) and new clusters (CO)₆Fe₂Se₂Mn₂(CO)₈ (5) and Cp"Re(CO)₂Se₂Fe₂(CO)₆ (6). By successive reactions of Mo(CO)₅THF with 1b and Fe₂Te₂(CO)₆, the new heterometallic heterochalcogenide cluster Fe₂(CO)₆(₃-Se)₂Mo(CO)₂(₃-Te)₂Fe₂(CO)₆ (8) was synthesized. The structures of 4b, 5, and 6 were determined by X-ray diffraction analysis.     

Some complexes containing carbon chains end-capped with tungsten or ruthenium groups and tricobalt carbonyl clusters

The Pd(0)/Cu(I)-catalysed reactions between Co₃(μ₃-CBr) (CO)₉ and W(CCCCH)(CO)₃Cp gives the C₅ complex {Cp(OC)₃W}CCCCC{Co₃(CO)₉} (2). Similarly, Co₃(μ₃-CBr)(μ-dppm)(CO)₇ and W(CCCCH)(CO)₃Cp or Ru(CCCCH)(dppe)Cp* give {Cp(OC)₃W}CCCCC{Co₃(μ-dppm)(CO)₇} and {Cp*(dppe)Ru}CCCCC{Co₃(μ-dppmn)(CO)₇} (5). An attempt to prepare a C₃ analogue from Ru(CCH)(PPh₃)₂Cp and Co₃(μ₃-CBr)(CO)₉ gave instead the acyl derivative {Cp(Ph₃P)₂Ru}CCC(O)C{Co₃(CO)₈(PPh₃)} (7). The X-ray structures of 2, 5 and 7 are reported: the C₅ chains in 2 and 5 have an essentially unperturbed -CC-CC-C formulation.     

Synthesis,characterization, and magnetochemical properties of two Mn4 clusters derived from 2-pyridinecarboxaldehyde Schiff base ligands

Two tetranuclear manganese complexes, [Mn₄(L¹)₆](ClO₄)₂?2.75H₂O (1) [HL¹ = 4-methyl-2-((pyridin-2-ylmethylene)amino)phenol] and [Mn₄(L²)₄(NO₃)₃(OH)]?pz?3H₂O (2) [HL² = (1H-pyrazol-1-yl)(pyridin-2-yl)methanol, pz = pyrazole], have been synthesized and characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and magnetic measurements. The structural analysis revealed that the central manganese ion is linked with three apical manganese ions through six phenoxo-bridges creating a Mn₄O₆ core for 1; 2 has a cubane-like topology with the Mn(II) ions and the deprotonated oxygens from L² alternatively occupying vertices. The magnetic studies indicated a weak ferromagnetic coupling interaction (J = 0.48 ± 0.087 cm^?1, g = 2.00, θ = ?0.78 K) for 1 and a weak antiferromagnetic spin-exchange interaction (J₁ = ?0.50 ± 0.075 cm^?1, J₂ = ?0.13 ± 0.082 cm^?1, g = 1.98) between Mn(II) ions for 2. The magnetostructural correlations of the two Mn₄ clusters have been discussed tentatively.     

Reactions of hydrosulfido- and hydroselenido-bridged dinuclear Ir, Rh, and Ru complexes with SbCl3 and BiCl3 affording mixed-metal sulfido and selenido clusters containing both noble metals and Group 15 metals

A new versatile method to synthesize a series of noble metal-Group 15 metal chalcogenido clusters has been found. Thus, treatment of the hydrosulfido- or hydroselenido-bridged dinuclear complexes [Cp*MCl(μ-EH)₂MCp*Cl] (M=Ir, Rh; E=S, Se; Cp*=η⁵-C₅Me₅), [Cp°RuCl(μ-SH)₂RuCp°Cl] (Cp°=η⁵-C₅EtMe₄), and [Ru(L)Cl(μ-SH)₂Ru(L)Cl] (L=η⁶-C₆Me₅H) with M^′Cl₃ (M^′=Sb, Bi) in THF at room temperature afforded smoothly the clusters [Cp*MCl(μ-EM^′Cl₂)₂MCp*Cl], [Cp°RuCl(μ-SM^′Cl₂)₂RuCp°Cl], and [Ru(L)Cl(μ-SM^′Cl₂)₂Ru(L)Cl] through dehydrochlorination. The X-ray analyses of eleven new clusters clarified the details of their structures consisting of the cubane-type M₂M^′₂E₂Cl₂ cores resulting from the presence of weak MCl?M^′ bonding interactions in addition to the normal M-E, M-Cl, and M^′-E bonds.     

Synthesis, characterization, and SAMs electroactivity of ruthenium complexes with sulfur containing ligands

The vibrational and ¹H NMR data hints that the coordination of the 2,2′-dithiodipyridine (2-pySS) ligand to the [Ru(CN)₅]³⁻ metal center occurs through the sulfur atom instead of the nitrogen atoms which is usually observed for N-heterocyclic ligands. Electrochemical results show that this coordination mode implies an additional thermodynamic stabilization of the Ru^II over Ru^III oxidation state due to a relative stronger π-back-bonding interaction with the empty low-lying dπ orbitals of the sulfur atom. Computational data reinforce the experimental results showing that the 2-pySS Lewis base centers are located on the sulfur atoms. Ligands containing only sulfur atoms as coordination sites (2,2′-dithiodipyridine N-oxide (2-pySSNO), 1,4-dithiane (1,4-dt), and 2,6-dithiaspiro[3.3]heptane (asp)) were also coordinated to the [Ru(CN)₅]³⁻ metal center to undoubtedly correlate the electrochemical results with the ligand coordination atom. Among the synthesized compounds, the [Ru(CN)₅(1,4-dt)]³⁻ and [Ru(CN)₅(asp)]³⁻ complexes showed to be able to form self-assembled monolayers (SAMs) on gold. These SAMs, which were characterized by SERS (surface-enhanced Raman scattering) spectroscopy, successfully assessed the heterogeneous electron transfer reaction of the cytochrome c metalloprotein in physiological medium.     

Syntheses,crystal structures,and photoluminescence of two new coordination polymers derived from dicarboxylate and N-donor ligands

Two metal-organic coordination polymers, [Co(tda)(ip)(H₂O)₂] _n (1) and [Mn(tda)(ip)(H₂O)] _n (2) [H₂tda?=?thiophene-2,5-dicarboxylic acid, ip?=?1H-imidazo[4,5-f][1,10]-phenanthroline], have been synthesized and characterized by elemental analyses, IR, PXRD, and X-ray diffraction. Single-crystal X-ray analyses reveal that 2,5-tda is a bridging ligand, exhibiting two coordination modes to link metal ions: μ₁-η¹?:?η⁰/μ₁-η¹?:?η⁰ and μ₂-η¹?:?η¹/μ₁-η¹?:?η⁰. Compound 1 demonstrates a 1-D structure in which Co²⁺ centers are connected via tda anions into 1-D chains; the chains are further connected via hydrogen-bonding and π?···?π interactions. Compound 2 displays a 2-D structure in which tda connects two Mn ions forming a dinuclear molecule. In 2 the 3-D supramolecular structure arrays through hydrogen-bonding and π?···?π interactions. In addition, photoluminescence for 1 and 2 is also investigated in the solid state at room temperature.     

Synthesis,characterization, and X-ray crystal structures of metal complexes with new Schiff-base ligands and their antibacterial activities

Two new potentially hexadentate Schiff bases, [H₂L¹] and [H₂L²], were prepared by condensation of 2-(3-(2-aminophenoxy)naphthalen-2-yloxy)benzenamine with 3,5-di-tert-butyl-2-hydroxy benzaldehyde and o-vanillin, respectively. Reaction of these ligands with cobalt(II) chloride, copper(II) perchlorate, and zinc(II) nitrate gave complexes ML. The ligands and their complexes have been characterized by a variety of physico-chemical techniques. The solid and solution state investigations show that the complexes are neutral. Molecular structures of [CuL¹], [CoL¹]?·?C₇H₈, and [ZnL²]?·?CH₃CN, which have been determined by single-crystal X-ray diffraction, indicate that [CuL¹] and [ZnL²]?·?CH₃CN display distorted square planar and distorted trigonal-bipyramidal geometry, respectively; the geometry around cobalt in [CoL¹]?·?C₇H₈ is almost exactly between trigonal bipyramidal and square pyramidal. The synthesized ligands and their complexes were screened for their antibacterial activities against eight bacterial strains and the ligands and complexes have antibacterial effects. The most effective ones are [CuL²] against Proteus vulgaris, Serratia marcescens, Staphylococcus subtilis, [H²L¹] against S. subtilis, and [H₂L²] against S. subtilis.     

Zn(II) complexes with pyridine derived N6 and N8 donor azamacrocyclic ligands

A novel N6 macrocyclic ligand, L¹ (2,8,14,20-tetramethyl-3,7,15,19,25,26-hexaaza-tricyclo[19.3.1.1^9,13]hexacosa-1(24),9,11,13(26),21(25),22-hexaene), was obtained by reduction of the 2 + 2 condensation product of 2,6-diacetylpyridine and propane-1,3-diamine. Zinc(II) complexes of L¹, of a related N8 macrocycle, L³ (3,6,9,17,20,23,29,30-octaaza-tricyclo[23.3.1.1[11,15]]triaconta-1(28),1,13,15(30),25(29),26-hexaene), similarly prepared by 2 + 2 condensation of 2,6-diformylpyridine and diethylenetriamine and of a tetra N-2-cyanoethyl derivative of a homologue of L¹ prepared from diformyl pyridine and ethane-1,2-diamine, L² (3-[6,14,17-tris-(2-cyano-ethyl)-3,6,14,17,23,24-hexaaza-tricyclo[17.3.1.1^8,12] tetracosa-1(23),8(24),9,11,19,21-hexaen-3-yl]-propionitrile), were prepared. Structures were determined for [ZnL¹](ClO₄)₂ · H₂O, [ZnL²](NO₃)₂ and [Zn₂L³(NO₃)₂](NO₃)₂ · H₂O. The [ZnL¹](ClO₄)₂ · H₂O and [ZnL²](NO₃)₂ complexes present a mononuclear endomacrocyclic structure with the metal in an octahedral distorted environment coordinated by the six donor nitrogen atoms from the macrocyclic backbone while the complex [Zn₂L³(NO₃)₂](NO₃)₂ · H₂O is dinuclear with both metal atoms into the macrocyclic cavity coordinated by four donor nitrogen atoms from the macrocyclic framework and one oxygen atom from one monodentate nitrate anion, in a distorted square pyramidal arrangement.     

Diorgano-gallium and -indium complexes with salen ligands: Synthesis, characterization, crystal structure and C-C coupling reactions

The reactions of triorgano-gallium and -indium etherate with salen ligands in benzene afforded complexes of the type [R₂MOC₆H₄CR′NCH₂-]₂, (R/M/R′ = Me/Ga/H (1), Et/Ga/H (2), Me/In/H (3), Et/Ga/Me (4)) in nearly quantitative yields. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR (¹H and ¹³C{¹H}) and mass spectral data. The organogallium complexes showed photoluminescence in blue-green region. The complex, [(Me₂Ga)₂(O-(C₆H₄)CHN-CH₂-)₂] on recrystallization from benzene-hexane and dichloromethane gave orthorhombic and monoclinic forms, respectively. Both the forms are dimeric with gallium atoms acquiring a distorted tetrahedral configuration defined by two methyl groups, phenolate oxygen and azomethene nitrogen. The complexes [(Me₂Ga)₂(O-(C₆H₄)CHN-CH₂-)₂] and [(Me₂In)₂(O-(C₆H₄)CHN-CH₂-)₂] have been employed as alkylating agent for C-C coupling reaction of 1-bromonaphthalene in presence of PdCl₂(PPh₃)₂.     

Synthesis,characterization, and cytotoxic and antimicrobial activities of ruthenium(II) arene complexes with N,N-bidentate ligands

Three new complexes, [(η⁶-C₆H₆)RuCl(C₅H₄N-2-CH=N-Ar)]PF₆ (Ar = phenylmethylene (1), (4-methoxyphenyl)methylene (2), and phenylhydrazone (3)), were prepared by reacting [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂ with N,N′-bidentate ligands in a 1 : 2 ratio. Full characterization of the complexes was accomplished using ¹H and ¹³C NMR, elemental and thermal analyses, UV–vis and IR spectroscopy and single crystal X-ray structures. Single crystal structures confirmed a pseudo-octahedral three-legged, piano-stool geometry around Ru(II), with the ligand coordinated to the ruthenium(II) through two N atoms. The cytotoxicity of the mononuclear complexes was established against three human cancer cell lines and selectivity was also tested against non-cancerous human epithelial kidney (HEK 293) cells. The compounds were selective toward the tumor cells in contrast to the known anti-cancer drug 5-fluoro uracil which was not selective between the tumor cells and non-tumor cells. All the compounds showed moderate activity against MCF7 (human breast adenocarcinoma), but showed low antiproliferative activity against Caco-2 and HepG2. Also, antimicrobial activities of the complexes were tested against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Of special interest is the anti-mycobacterial activity of all three synthesized complexes against Mycobacterium smegmatis, and bactericidal activity against resistant Enterococcus faecalis and methicillin-resistant Staphylococcus aureus ATCC 43300.     

Octaalkylphthalocyaninato ruthenium(II) complexes with mixed axial ligands and supramolecular porphyrin:phthalocyanine structures derived from them

Complementary syntheses of 1,4,8,11,15,18,22,25-octakis(alkyl) substituted ruthenium phthalocyanines, in which either one or two axial ligands can be added, are described. Their utility in the preparation of further (pyridyl) ligated derivatives has been shown to be straightforward. The chemistry is sufficiently robust and efficient to permit elaborate, supramolecular complexes to be prepared, as demonstrated by the synthesis of porphyrin-phthalocyanine multichromophore arrays.     

Hydrothermal synthesis,crystal structures,and photoluminescent properties of two cadmium(II) coordination polymers derived from dicarboxylates and N-donor ligands

Two metal coordination polymers, [Cd(ipa)(L₁)(H₂O)]_n (1) and [Cd(ipa)(L₂)]_n (2) [H₂ipa?=?isophthalic acid, L₁?=?3,5-bis(imidazole-1-yl)pyridine and L₂?=?3,5-bis(benzoimidazo-1-ly)pyridine], have been synthesized and structurally characterized by IR, elemental analysis, XRD, and X-ray single-crystal diffraction. Complex 1 shows a twofold cds topological net and 2 features a 3-D pcu topological net. Luminescent properties of 1 and 2 were investigated in the solid state at room temperature.     

Two Cd(II) complexes derived from mercapto-triazole ligands: syntheses,crystal structures,and luminescent properties

Two cadmium complexes, {[Cd(a-ptt)(ptt)]·H₂O} _n (1) and [Cd(a-Hmtt)₂(SO₄)H₂O]·CH₃OH (2), have been prepared based on 4-amino-3-(4-pyridine)-5-mercapto-1,2,4-triazole (a-Hptt) and 4-amino-3-methyl-5-mercapto-1,2,4-triazole (a-Hmtt), respectively. In 1, amino-triazole ligand a-Hptt can partly be deaminated and transformed into 3-(4-pyridine)-5-mercapto-triazole (Hptt) under hydrothermal conditions. X-ray diffraction analysis reveals that 1 exhibits an unusual 2-D lampshade-type layer structure in which the amino ligand a-ptt and the deamination ligand ptt display exo-tridentate bridging and bidentate bridging, respectively. Complex 2 is mononuclear and further assembled into a 3-D supramolecular architecture via non-covalent interactions. Complexes 1 and 2 were characterized by elemental analyses, IR, and thermogravimetric analyses. Furthermore, solid-state luminescent properties of 1 and 2 have also been investigated.     

Metal complexes derived from hydrazoneoxime ligands: IV. Molecular and supramolecular structures of some nickel(II) complexes derived from diacetylmonoxime S-benzyldithiocarbazonate

Four new nickel(II) complexes, [{Ni(L)}₂], [NiL · HPyr], [NiL · HIm] and [Ni(HL)₂] · H₂O, derived from diacetylmonoxime-S-benzyldithiocarbazonate (H₂L) have been synthesized and characterized by elemental analyses, field desorption and electrospray ionization mass spectra, UV–Vis, infrared absorption spectra, as well as ¹H NMR spectra. X-ray molecular structures showed that the Ni(II) in both [NiL · HPyr] and [NiL · HIm] are in a distorted square planar environment and is coordinated to the dianionic NNS tridentate hydrazoneoxime ligand via deprotonated oximate nitrogen, hydrazone imine nitrogen, and thiolate sulphur. The fourth coordination sites are occupied, respectively, by the pyrazole and imidazole nitrogens. The oximate O1 of [NiL · HPyr] is involved in intramolecular hydrogen bond with the pyrazole NH proton as well as intermolecular hydrogen bond pyrazole C6H proton, forming a helical chain propagating along the b-axis. The structure is stabilized by a set of π?π and CH?π interactions. The molecular units in [NiL · HIm] are linked together by hydrogen bond formation between the oximate oxygen and imidazole NH proton, giving rise to an infinite zigzag chain extended along the a-axis. The chains are interconnected by π?π and CH?O interactions. In [Ni(HL)₂] · H₂O, the Ni(II) is in a distorted octahedral environment. The two mononegative hydrazoneoxime ligands are coordinated in the meridional configuration where the two thiol sulphur atoms and the two oxime nitrogen atoms are cis to each other, while the imine nitrogen atoms are trans. The oxime proton O2H is involved in a reciprocal bifurcated hydrogen bond formation with both N2 and S3 of the adjacent molecule giving rise to hydrogen bonded dimer. This dimeric structure is further stabilized by a pair of reciprocal CH?O interactions. A one dimensional chain of alternating dimeric unit and water molecule propagating along the c-axis is formed via hydrogen bond formation between the oxime O1 oxygen and the bridged water molecule proton.     

Synthesis, characterization, reactivity and computational studies of new rhenium(I) complexes with thiosemicarbazone ligands derived from 4-(methylthio)benzaldehyde

N-thioamide thiosemicarbazone derived from 4-(methylthio)benzaldehyde (R = H, HL¹; R = Me, HL² and R = Ph, HL³) have been prepared and their reaction with fac-[ReX(CO)₃(CH₃CN)₂] (X = Br, Cl) in methanol gave the adducts [ReX(CO)₃(HLⁿ)] (1a X = Cl, n = 1; 1a′ X = Br, n = 1; 1b X = Cl, n = 2; 1b′ X = Br, n = 2; 1c X = Cl, n = 3; 1c′ X = Br, n = 3) in good yield.All the compounds have been characterized by elemental analysis, mass spectrometry (ESI), IR and ¹H NMR spectroscopic methods. Moreover, the structures of HL², HL³, HL³·(CH₃)₂SO and 1b′·H₂O were also elucidated by X-ray diffraction. In 1b′, the rhenium atom is coordinated by the sulphur and the azomethine nitrogen atoms (κS,N³) forming a five-membered chelate ring, as well as three carbonyl and bromide ligands. The resulting coordination polyhedron can be described as a distorted octahedron.The structure of the dimers is based on rhenium(I) thiosemicarbazonates [Re₂(L¹)₂(CO)₆] (2a), [Re₂(L²)₂(CO)₆] (2b) and [Re₂(L³)₂(CO)₆] (2c) as determined by X-ray studies. Methods of synthesis were optimized to obtain amounts of these thiosemicarbazonate complexes. In these compounds the dimer structures are achieved by Re-S-Re bridges, where S is the thiolate sulphur from a κS,N³-bidentate thiosemicarbazonate ligand.Some single crystals isolated in the synthesis of 2b contain [Re(L⁴)(L²)(CO)₃] (3b) where L⁴ (=2-methylamine-5-(para-methylsulfanephenyl)-1,3,4-thiadiazole) is originated in a cyclization process of the thiosemicarbazone. Furthermore, the rhenium atom is coordinate by the sulphur and the thioamidic nitrogen of the thiosemicarbazonate (κS,N²) affording a four-membered chelate ring.     

Syntheses,characterization and X-ray crystal structures of Co(III) and Mn(II) complexes of pyrimidine derived Schiff base ligands

Two pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₁] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₂] have been synthesised by 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. One Co(III) and one Mn(II) complex of HL₁ and one Mn(II) complex of HL₂ have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N₄S₂ chromophore around the central metal ion. Each ligand molecule binds the metal ion using pyrimidyl nitrogen, azomethine nitrogen and the thiolato sulfur atoms. In the free ligand moieties, the pyrimidine nitrogen atoms, azomethine nitrogen atoms and thione sulfur atoms are in EEE orientation to each other. During chelation, all the donor sites of the ligands are reoriented to ZEZ configuration in order to facilitate the chelation process. In all the complexes, the respective ligand molecule functions as the monoanionic tridentate one. All complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from octahedral geometry of the coordination environment were observed.     

Chalcogen-capped ruthenium carbonyl clusters derived from diphosphazane mono- and dichalcogenides of the type X2P(E)N(R)PX2 and X2P(E)N(R)P(E)X2 (E = S or Se)

Reactions of Ru₃(CO)₁₂ with diphosphazane monoselenides Ph₂PN(R)P(Se)Ph₂ [R = (S)-∗CHMePh (L⁴), R = CHMe₂ (L⁵)] yield mainly the selenium bicapped tetraruthenium clusters [Ru₄(μ₄-Se)₂(μ-CO)(CO)₈{μ-P,P-Ph₂PN(R)PPh₂}] (1, 3). The selenium monocapped triruthenium cluster [Ru₃(μ₃-Se)(μ_sb-CO)(CO)₇{κ²-P,P-Ph₂PN((S)-∗CHMePh)PPh₂}] (2) is obtained only in the case of L⁴. An analogous reaction of the diphosphazane monosulfide (PhO)₂PN(Me)P(S)(OPh)₂ (L⁶) that bears a strong π-acceptor phosphorus shows a different reactivity pattern to yield the triruthenium clusters, [Ru₃(μ₃-S)(μ₃-CO)(CO)₇{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (9) (single sulfur transfer product) and [Ru₃(μ₃-S)₂(CO)₅{κ²-P,P-(PhO)₂PN(Me)P(OPh)₂}{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (10) (double sulfur transfer product). The reactions of diphosphazane dichalcogenides with Ru₃(CO)₁₂ yield the chalcogen bicapped tetraruthenium clusters [Ru₄(μ₄-E)₂(μ-CO)(CO)₈{μ-P,P-Ph₂PN(R)PPh₂}] [R = (S)-∗CHMePh, E = S (6); R = CHMe₂, E = S (7); R = CHMe₂, E = Se (3)]. Such a tetraruthenium cluster [Ru₄(μ₄-S)₂(μ- CO)(CO)₈{μ-P,P-(PhO)₂PN(Me)P(OPh)₂}] (11) is also obtained in small quantities during crystallization of cluster 9. The dynamic behavior of cluster 10 in solution is probed by NMR studies. The structural data for clusters 7, 9, 10 and 11 are compared and discussed.