Synthesis,characterization and acceptor behavior of n-butyltin(IV)-2,4-dimethylphenoxides

The n-butyltin(IV) complexes, n-BuSnCl_3?x(OC₆H₃(CH₃)₂-2,4) _x (where x?=?1–3), have been synthesized in quantitative yields by employing the reaction of n-BuSnCl₃ with 2,4-dimethylphenol and sodium acetate in methanol and benzene solvents at room temperature. The complexes have been characterized by elemental analysis, molar conductivity, and FT-IR, ¹H- and ¹³C-NMR, and mass spectral studies. Thermal behavior has been studied by TG–DTA techniques. Lewis acid character of n-BuSn(OC₆H₃(CH₃)₂-2,4)₃ has been investigated by reacting it with bases such as 2,2′-bipyridine and 1,10-phenanthroline (B), Ph₃PO and Ph₃AsO (LO) and phosphorus and arsenic donors Ph₃P, Ph₃As, and As(SPh)₃ (L). The formation of 1?:?1 and 1?:?2 (metal?:?base) coordination compounds [n-BuSn(OC₆H₃(CH₃)₂-2,4)₃·B] and n-[BuSn(OC₆H₃(CH₃)₂-2,4)₃·2LO/2L] has been authenticated by physicochemical and IR spectral studies. In order to infer the biological relevance of newly synthesized complexes, the antibacterial activity has been assayed against six bacterial strains Klebsiella pneumoniae, Staphylococcus epidermidis, Staphylococcus aureus, Salmonella typhi, Salmonella paratyphi, and Escherichia coli. In this study, n-BuSnCl₂(OC₆H₃(CH₃)₂-2,4) and n-BuSnCl(OC₆H₃(CH₃)₂-2,4)₂ showed better activity than precursor and ligand, while n-BuSn(OC₆H₃(CH₃)₂-2,4)₃ did not exhibit improved activity.     

Thermoanalytical investigations of niobium(V) complexes of 4-isopropylphenol

Thermal behaviour of newly synthesized niobium(V) aryloxides of composition [NbCl_5−n (OC₆H₄CH(CH₃)₂-4) _n ] (where n = 1 → 5) synthesized by the reactions of niobium pentachloride with 4-isopropylphenol in predetermined molar ratios in carbon tetrachloride has been studied by thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The results showed that thermal decomposition of complex of composition [NbCl₄(OC₆H₄CH(CH₃)₂-4)] resulted in the formation of NbOCl₃ as the ultimate decompositional product while all other complexes yielded Nb₂O₅ as the final product of thermal decomposition. From the mathematical analysis of TG data, the kinetic and thermodynamic parameters viz. energy of activation, frequency factor, entropy of activation, etc. have been evaluated using Coats–Redfern equation.     

Rhenium(I) and Technetium(I) Tricarbonyl Complexes with Phosphoraneimines

[NEt₄]₂[Re(CO)₃Br₃] and [NEt₄]₂[Tc(CO)₃Cl₃] react with trimethylsilyltriphenylphosphoraneimine, Me₃SiNPPh₃, under exchange of the bromo ligands and the formation of cationic [M(CO)₃(HNPPh₃)₃]⁺ complexes (M = Re, Tc). The required protons are abstracted from the solvent CH₂Cl₂. The steric bulk of the organic ligands causes a marked distortion of the established coordination polyhedra from an idealized octahedron with bond angles between neighbouring donor atoms between 81.81(8)° and 96.66(8)°. The reaction of [NEt₄]₂[Re(CO)₃Br₃] with Me₃SiNP(Ph₂)CH₂PPh₂ in CH₂Cl₂ yields the neutral complex [Re(CO)₃Br{HNP(Ph₂)CH₂PPh₂)], which contains a neutral, chelate‐bonded (diphenylphosphinomethyl)diphenylphosphoraneimine ligand. A similar reaction with the bifunctional phosphoraneimine Me₃SiNP(Ph₂)CH₂(Ph₂)PNSiMe₃ gives only small amounts of a binuclear rhenium(I) complex of the composition [{Re(CO)₃Br₂}₂(HNP(Ph₂)CH₂(Ph₂)PNH)]^2‐, whereas the major amount of the bis‐phosphoraneimine undergoes an intramolecular rearrangement to yield [H₂NP(Ph₂)NP(Ph₂)CH₃]Br. An X‐ray structure analysis shows a widespread delocalization of electron density over the central part of the cation.     

Synthesis,characterization, reactivity,and antifungal activity of chlorobis(2,4-dinitrophenoxo) monooxovanadium(V)

[VOCl(OC₆H₃(NO₂)₂-2,4)₂] (1) has been synthesized by the reaction of VOCl₃ with bimolar amounts of Me₃SiOC₆H₃(NO₂)₂-2,4 in toluene and characterized by elemental analyses, molar conductance, infrared (IR), ¹H and ¹³C NMR and mass spectral, and thermal studies. Molecular modeling dynamics of the complex suggests tetrahedral geometry around vanadium. The reaction of 1 with sodium alkoxides, NaOR (OR?=?OMe (methoxy); OEt (ethoxy), OBuⁿ(n-butoxy); OPrⁱ (isopropoxy); and OAmⁱ(isoamyloxy)) afforded mixed alkoxo–phenoxo complexes, [VO(OR)(OC₆H₃(NO₂)₂-2,4)₂] authenticated by physicochemical and IR spectral studies. The antifungal activities of the ligand and complexes against three fungi, namely Aspergillus niger, Byssachlamys fulva, and Mucor circinelloides have been assayed by the minimum inhibitory concentration method. The complexes have improved antifungal activity compared to free ligand.     

Chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ2P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate

The aminophosphane ligand 1‐amino‐2‐(diphenylphosphanyl)ethane [Ph₂P(CH₂)₂NH₂] reacts with dichloridotris(triphenylphosphane)ruthenium(II), [RuCl₂(PPh₃)₃], to form chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ²P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate, [RuCl(C₁₈H₁₅P)(C₁₄H₁₆NP)₂]Cl·C₇H₈ or [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]Cl·C₇H₈. The asymmetric unit of the monoclinic unit cell contains two molecules of the Ru^II cation, two chloride anions and two toluene molecules. The Ru^II cation is octahedrally coordinated by two chelating Ph₂P(CH₂)₂NH₂ ligands, a triphenylphosphane (PPh₃) ligand and a chloride ligand. The three P atoms are meridionally coordinated, with the Ph₂P– groups from the ligands being trans. The two –NH₂ groups are cis, as are the chloride and PPh₃ ligands. This chiral stereochemistry of the [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]⁺ cation is unique in ruthenium–aminophosphane chemistry.     

Linking of CuI Units by Tetrahedral Mo2E2 Complexes (E=P,As)

The reaction of [Cp₂Mo₂(CO)₄(μ,η^2:2-E₂)] ( A : E=P, B : E=As, Cp=C₅H₅) with the WCA-containing Cu^I salts ([Cu(CH₃CN)₄][Al{OC(CF₃)₃}₄] (CuTEF, C ), [Cu(CH₃CN)₄][BF₄] ( D ) and [Cu(CH₃CN)_3.5][FAl{OC₆F₁₀(C₆F₅)}₃] (CuFAl, E )) affords seven unprecedented coordination compounds. Depending on the E₂ ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu₃ arrays linked by E₂ units (E=P, As) coordinated in an η^2:1:1 coordination mode. All compounds were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu⋅⋅⋅Cu⋅⋅⋅Cu interactions, DFT calculations were performed.     

Thermoanalytical investigations of niobium(V) chloride aryloxides

Niobium(V) chloride aryloxides [NbCl₃(OAr)₂] and [NbCl₂(OAr)₃] (Oar = —OC₆H₄Bu ^t -4 and —OC₆H₄OMe-4) have been prepared by reacting NbCl₅ with two and three equivalents of the respective phenol in CCl₄. The complexes have been characterized by elemental analysis, molecular weight determination, i.r., ¹H-n.m.r., u.v.–vis. and MS techniques. Thermal behaviour (t.g.–d.t.) of the complexes has also been studied and decomposition schemes proposed. The kinetic and thermodynamic parameters namely, the activation energy 'E ^*', the frequency factor 'A', entropy of activation 'S' and specific rate constant 'kr' etc. have been calculated employing the Coats–Redfern equation. The non-isothermal t.g. data has also been utilized to determine the most probable mechanism and corresponding activation energy for the decomposition of niobium(V) complexes by testing seven different theoretically possible decomposition mechanisms.     

Aryl- und Arin-Komplexe von Übergangsmetallen der sechsten Gruppe Darstellung von [Mo(p-C6H4CH3)6(Li · OC4H10)3] und [W(p-C6H4CH3)4(C6H3CH3)2(Li · OC4H10)4] sowie NMR-spektroskopische Untersuchung des W-Komplexes

Aryl and Aryne Complexes of Group Six Transition Metals. Preparation of [Mo(p-C₆H₄CH₃)₆(Li · OC₄H₁₀)₃] und [W(p-C₆H₄CH₃)₄(C₆H₃CH₃)₂(Li · OC₄H₁₀)₄] and NMR Spectroscopic Investigation of the W Complex Molybdenum(V) chloride reacts with an etheral solution of p-tolyllithium (molar ratio 1:10) to yield a yellow, strongly paramagnetic hexatolylo complex ([MoTol₆(Li · S)₃]¹) (μ_eff = 3.51 B.M.), while from tungsten(V) bromide and p-tolyllithium (molar ratio 1:11) a blackish violet, diamagnetic complex [WTol₄Tn₂(Li · S)₄] is formed, containing two tolylene or tolyne groups for ligands. The ¹H-NMR spectrum points to the Tol-ligands being influenced by the methyl groups of the Tn-ligands.     

Spectral and crystallography studies of new palladacycle complexes with P,C‐ and C,C‐donor ligands; Application of (OAL16) to optimizing the yield of Mizoroki‐Heck reaction

The new symmetrical diphosphonium salt [Ph₂P(CH₂)₂PPh₂(CH₂C(O)C₆H₄Br)₂] Br₂ ( S ) was synthesized in the reaction of 1,2‐bis (diphenylphosphino) ethane (dppe) and related ketone. Further treatment with NEt₃ gave the symmetrical α‐keto stabilized diphosphine ylide [Ph₂P(CH₂)₂PPh₂(CHC(O)C₆H₄Br)₂] ( Y ¹ ). The unsymmetrical α‐keto stabilized diphosphine ylide [Ph₂P(CH₂)₂PPh₂(CHC(O)C₆H₄Br)] ( Y ² ) was synthesized in the reaction of diphosphine in 1:1 ratio with 2.3′‐dibromoacetophenone, then treatment with NEt_3. The reaction of dibromo (1,5‐cyclooctadiene)palladium (II), [PdBr₂(COD)] with this ligand ( Y ¹ ) in equimolar ratio gave the new C,C‐chelated [PdBr₂(Ph₂P(CH₂)₂PPh₂(C(H)C(O)C₆H₄Br)₂)] ( 1 ) and with unsymmetrical phosphorus ylide [Ph₂P(CH₂)₂PPh₂C(H)C(O)C₆H₄Br] ( Y ² ) gave the new P, C‐chelated palladacycle complex [PdBr₂(Ph₂P(CH₂)₂PPh₂C(H)C(O)Br)] ( 2 ). These compounds were characterized successfully by FT‐IR, NMR (¹H, ¹³C and ³¹P) spectroscopic methods and the crystal structure of Y ¹ and 2 were elucidated by single crystal X‐ray diffraction. The results indicated that the complex 1 was C, C‐chelated whereas complex 2 was P, C‐chelated. These air/moisture stable complexes were employed as efficient catalysts for the Mizoroki‐Heck cross‐coupling reaction of several aryl chlorides, and the Taguchi method was used to optimize the yield of Mizoroki‐Heck coupling. The optimum condition was found to be as followed: base; K₂CO₃, solvent; DMF and loading of catalyst; 0.005 mmol.     

Phosphaniminato-Komplexe von Niob und Tantal. Die Kristallstrukturen von [NbCl4(NPiPr3)(CH3CN)], [NbCl3(NPiPr3)2], [TaCl4(NPiPr3)]2 und [TaCl3(NPiPr3)2]

Phosphorane Iminato Complexes of Niobium and Tantalum. Crystal Structures of [NbCl₄(NPⁱPr₃)(CH₃CN)], [NbCl₃(NPⁱPr₃)₂], [TaCl₄(NPⁱPr₃)]₂, and [TaCl₃(NPⁱPr₃)₂] The title compounds have been prepared from the pentachlorides of niobium and tantalum with the silylated phosphorane imine Me₃SiNPⁱPr₃. They are characterized by IR spectroscopy and crystal structure determinations. NbCl₄(NPⁱPr₃)(CH₃CN)] . Space group Pna2₁, Z = 4, 2102 observed unique reflections, R = 0.022. Lattice dimensions at ?50°C: a = 1627.2, b = 876.3, c = 1335.3 pm. The compound forms monomeric molecules with the acetonitrile molecule in trans position to the phosphorane iminato group. This group shows a short NbN distance of 178.2 pm with a NbNP bond angle of 165.2°. [NbCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 2534 observed unique reflections, R = 0.046. Lattice dimensions at 20°C: a = 1302.65, b = 1321.69, c = 1672.04 pm, β = 111.713°. The compound forms monomeric molecules with a distorted bipyramidal surrounding of the niobium atom and equatorially arranged phosphorane iminato groups. [TaCl₄(NPⁱPr₃)]₂ . Space group Pbca, Z = 4, 1537 observed unique reflections, R = 0.037. Lattice dimensions at ?40°C: a = 1420.6, b = 1483.9, c = 1622.0 pm. The compound forms centrosymmetric dimeric molecules with dissimilarly long Ta₂Cl₂ bridges and equatorially arranged phosphorane iminato groups. [TaCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 5737 observed unique reflections, R = 0.039. Lattice dimensions at ?50°C: a = 1303.9, b = 1327.2, c = 1682.1 pm, β = 111,92°. The compound is isotypical with the corresponding niobium compound.     

Synthesis of bridged and linked ruthenium and osmium carbonyl clusters containing a [Au2(Ph2PCH2CH2PPh2)]2+ unit. The crystal and molecular structures of Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) and {Os4H3(CO)12}2Au2(Ph2PCH2CH2PPh2)

Treatment of Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂ with one equivalent of the [Ru₅C(CO)₁₄]²⁻ dianion in the presence of TlPF₆ gives Ru₅C(CO)₁₄Au₂(Ph₂PCH₂CH₂PPh₂) (1) in good yield and the [{Ru₅C(CO)₁₄}₂Au₂(Ph₂PCH₂CH₂PPh₂)]²⁻ (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru₅C(CO)₁₄]²⁻ are used. Reaction of [Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂] with 3 equivalents of [H₃Os₄(CO)₁₂]⁻ anion in the presence of TlPF₆ affords {H₃Os₄(CO)₁₂}₂Au₂(Ph₂PCH₂CH₂PPh₂) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au₂(Ph₂PCH₂CH₂PPh₂)]²⁺ fragment in different coordination modes.     

Synthesis, Characterization of Mixed Ligand Palladium(II) Complexes of Triphenylphosphine and Anilines and their Enzyme Inhibition Studies against β-glucuronidase. The Crystal Structure of trans-dichloro-(m-chloroaniline)(triphenylphosphine)palladium(II)

A number of palladium(II) complexes with Ph₃P and aromatic amines as ligands having the general formula [(Ph₃P)Pd(Ph₃P)(NH₂R)Cl₂] {where R = Ph (1), m-ClC₆H₄ (2), p-ClC₆H₅ (3)} and [Pd(CH₃NHPh)Cl₂] (4), have been synthesized and characterized by elemental analysis, IR, ¹H and ¹³C NMR. The X-ray crystal structure of [(Ph₃P)Pd(m-ClC₆H₄NH₂)Cl₂] · CH₂ Cl₂ (2) shows a distorted square planar environment around the Pd(II) ion with the P–Pd–N and Cl(1)–Pd–Cl(2) bond angles of 174.88(5)° and 176.77(2)° respectively. The complexes were screened for enzyme inhibition activity against β-glucuronidase and found to be active.     

Bis(triphenylphosphaniminato)niobtrichlorid, [NbCl3(NPPh3)2], ein Komplex mit fünffach koordiniertem Niob

Bis(triphenylphosphorane-iminato)niobium Trichloride, [NbCl₃(NPPh₃)₂], a Complex with Coordination Number Five at the Niobium Atom The title compound has been prepared from niobium pentachloride with Me₃SiNPPh₃ in acetonitrile solution, forming colourless, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. [NbCl₃(NPPh₃)₂] crystallizes monoclinically in the space group Cc with four formula units per unit cell, 3682 observed, unique reflections, R = 0.042%. Lattice dimensions at 20°C: a = 1025.1(2); b = 1870.6(6); c = 1832.5(5) pm, β = 91.83(2)°. The niobium atom of the complex is coordinated in a distorted trigonal bipyramidal fashion, while the nitrogen atoms of the two phosphorane iminato ligands are in equatorial position along with one chlorine atom. NbN and PN distances accord with double bonds; with a mean value of 242.0 pm the Nb Cl distances are remarkably long.     

Isolation of a Dodecanuclear Polyoxo Cluster {Nb12O21} Showing a Rare Case of Five-fold Coordinated Niobium(V) Centers with a Square Pyramidal Geometry

The reactivity of the complexing anthracene-9-carboxylate ligand has been investigated with a niobium(IV) tetrachloride precursor (NbCl₄ ⋅ 2THF) in isopropanol solvent. This resulted in the crystallization of a molecular assembly containing two distinct {Nb₁₂O₂₁} cores surrounded by multiple isopropanolate and anthracenoate ligands. The compound is formulated [Nb₁₂₍(μ₃-O)₃(μ-O)₁₈(C₁₅H₉O₂)₈(OⁱPr)₁₀] ⋅ [Nb₁₂(μ₃-O)₂(μ-O)₁₉(C₁₅H₉O₂)₈(OⁱPr)₁₀] illustrating the two different dodecameric oxo-clusters, for which the niobium(IV) precursor was oxidized in the niobium(V) state during the reactional process. The two distinct {Nb₁₂O₂₁} units mainly differs by the environment of the niobium centers, which exhibits unexpected five-fold coordination (square pyramid) for some of them, together with the classical six-fold coordination (octahedron) as usually found for niobium(V). In the crystallization process, the. IR spectroscopy was used to analyze the esterification reaction occurring between the anthracene acid an isopropanolate ligands responsible of the production of water used in the oxo-condensation of the niobium centers. ⁹³Nb Solid state NMR was tentatively used to assess the occurrence of the different niobium environments.     

On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

The reaction of the electronically unsaturated platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) with Ph₂PCH₂CH₂CH₂SPh ( 2 ) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 4 ) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 6 ). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH₂CH₂CH₂SO₂Ph ( 3 ) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 5 ). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 8 ) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)] ( 7 ) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂][BF₄] ( 9 ). All complexes were characterized by microanalysis and NMR spectroscopy (¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Synthesis and characterization of silver(I) complexes with N‐thiophosphorylated thiobenzamide or thiourea and phosphines

A reaction of the potassium salts of RC(S)NHP(S)(OiPr)₂ (R = PhNH, HL ^I; Ph, HL ^II) with a mixture of AgNO₃ and Ph₂P(CH₂)_{1 − 3}PPh₂ or Ph₂P(C₅H₄FeC₅H₄)PPh₂ in aqueous EtOH/CH₂Cl₂ leads to [Ag₂(Ph₂PCH₂PPh₂)₂L^INO₃] ( 1 ), [Ag{Ph₂P (CH₂)₂PPh₂}L^I,II] ( 2, 6 ), [Ag{Ph₂P(CH₂)₃PPh₂}L^I,II] ( 3, 7 ), [Ag{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^I,II] ( 4, 8 ), and [Ag₂(Ph₂PCH₂PPh₂)L^II₂] ( 5 ) complexes. The structures of these compounds were investigated by ¹H and ³¹P{¹H} NMR spectroscopy and elemental analyses. It was established that the binuclear complexes 1 and 5 are luminescent in the solid state at ambient conditions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:386–391, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20627     

Polymere Thiolatokomplexe [M(SPh)3]∞ der Metalle Molybdän,Wolfram, Eisen und Ruthenium mit linearen Metallketten. Synthese und Struktur von (OC)3Fe(SPh)3Fe(SPh)3Fe(CO)3 · 2(CH3)2CO

Polymeric Thiolato Complexes [M(SPh)₃]∞ of the Metals Mo, W, Fe, and Ru with Linear Metal Chains. Synthesis and Crystal Structure of (OC)₃Fe(SPh)₃Fe(SPh)₃Fe(CO)₃ · 2(CH₃)₂CO At high temperature the reaction of the metal carbonyls Mo(CO)₆, W(CO)₆ and Fe(CO)₅ with S₂Ph₂ (Ph = C₆H₅) yields the polymeric complexes [M(SPh)₃]∞. Similarly [Ru(SPh)₃]∞ can be obtained from ruthenium(III) acetylacetonate and HSPh. At room temperature under UV-irradiation Fe(CO)₅ reacts with S₂Ph₂ to form the oligomeric complex (OC)₃Fe(SPh)₃Fe(SPh)₃Fe(CO)₃. The polymeric complexes [M(SPh)₃]∞ (M = Mo, W, Fe, Ru) are composed of linear chains with bridging SPh-ligands between the metal atoms. Of these complexes [Fe(SPh)₃]∞ is paramagnetic, whereas the others exhibit antiferromagnetic behaviour. The spin coupling is presumably connected with the formation of metal pairs, resulting in alternating shortened and extended distances in the metal chain. The oligomeric complex (OC)₃Fe(SPh)₃Fe(SPh)₃Fe(CO)₃ crystallizes triclinic in the space group P1 with z = 2. It has almost the symmetry D_3d with a linear arrangement of the Fe atoms. The paramagnetism of Fe₃(CO)₆(SPh)₆ can be explained by a d⁶ high spin configuration of the central atom and low spin behaviour of the two other Fe atoms, which are bonded to CO.     

Copper(II) and Cadmium(II) Complexes Based on N,N‐Bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine Ligand: Syntheses,Structures, Magnetic,and Luminescent Properties

The reaction of the aryl‐oxide ligand H₂L [H₂L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO₄ · 5H₂O, CuCl₂ · 2H₂O, CuBr₂, CdCl₂ · 2.5H₂O, and Cd(OAc)₂ · 2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂] · SO₄ · 3CH₃OH ( 1 ), [Cu₂(H₂L²)₂Cl₄] ( 2 ), [Cu₂(H₂L²)₂Br₄] ( 3 ), [Cd₂(HL)₂Cl₂] ( 4 ), and [Cd₂(L)₂(CH₃COOH)₂] · H₂L ( 5 ), where H₂L¹ [H₂L¹ = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H₂L² [H₂L² = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.     

Vinylmetallics as ligands. VI. Preparation and stabilities of a series of vinylsilane-platinum (0) complexes

A series of complexes of formula, [(Ph₃P)₂PtCH₂=CHSi (CH₃)_n(OC₂H₅)_3---n] (n = 0,1,2,3), has been prepared and characterized. The all carbon compound, [(Ph₃P)₂PtCH₂=CHC (CH₃)₃], has also been prepared and found to decompose in solution much more readily than its silicon analogue.