Coordination complexes of PdII with benzothiazolines

Summary Some new Pd^II complexes have been synthesized by reacting PdCl₂ with monofunctional bidentate Schiff bases (condensation product of furfuraldehyde, pyridine-2-aldehyde and thiophene-2-aldehyde witho-amino-thiophenol) in different molar ratios. The i.r. and n.m.r. spectra reveal that the nitrogen of azomethine and sulphur of thiol are coordinating sites. Electronic spectral data suggests square planar geometry for these complexes.     

Synthesis,spectroscopic, thermal,crystal structure properties,and characterization of new Hofmann-Td-type complexes with 3-aminopyridine

In this study, synthesis of two new tetracyanocadmate(II) and tetracyanozincate(II) complexes based on 3-aminopyridine (3AP) and investigation of their structural properties were reported. These complexes were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Investigation of the elemental, spectral and single crystal data of these complexes showed that the formulas [Cd(3AP)₂Zn(μ₄-CN)₄]_n (1) and [Cd(3AP)₂Cd(μ₄-CN)₄]_n (2) fully explained their crystal structure. General information about the structural and chemical properties of these complexes obtained in single crystal form was obtained by observing the changes in the characteristic peaks of the 3AP with the [Zn(μ₄-CN)₄]^2- and [Cd(μ₄-CN)₄]^2- structures that make up these complexes. The behaviors of these complexes against changes in temperature were obtained by examining the temperature-dependent changes of their mass. The asymmetric unit of the heterometallic complexes 1 and 2 consist of half Cd(II) ion, half M ion [M = Zn1 in 1 and Cd2 in 2], two cyanide ligands and one 3AP.     

Synthesis and spectroscopic studies of the charge transfer complexes of 2- and 3-aminopyridine

The interactions of the electron donors 2-aminopyridine (2APY) and 3-aminopyridine (3APY) with the π-acceptors tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 2-chloro-1,3,5-trinitrobenzene (picryl chloride, PC), and 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge transfer (CT) complexes were recorded. Photometric titration showed that the stoichiometries of the reactions were fixed and depended on the nature of both the donor and the acceptor. The molecular structures of the CT-complexes were, however, independent of the position of the amino group on the pyridine ring and were formulated as [(APY)(TCNE)], [(APY)(DDQ)], [(APY)(PC)], and [(APY) (chloranil)]. The formation constants (K_CT), charge transfer energy (E_CT) and molar extinction coefficients (_CT) of the formed CT-complexes were obtained.     

聚-2-氨基吡啶电化学合成及性质

报导了在 0.43 mol•dm－3 C6H6N2和0.01 mol•dm－3 NaOH中用循环伏安法合成聚-2-氨基吡啶. 聚-2-氨基吡啶在1.0 mol•dm－3 ZnCl2(pH=4.99)溶液中的循环伏安图上有三对氧化-还原峰.旋转环-盘实验的结果表明,在 2-氨基吡啶聚合的初期有中间体生成.由红外光谱可知，聚-2-氨基吡啶具有头-尾相接的结构.聚-2-氨基吡啶平均粒子大小约893 nm， 平均粒子间距约 255 nm. 由聚-2-氨基吡啶正极和锌负极及2.5 mol•dm－3 ZnCl2溶液和 3.0 mol•dm－3 NH4Cl (pH=5.5) 溶液构成的电池，其放电曲线类似于Li-SOCl2, 放电曲线的中间区域非常平稳.     

Synthesis and characterization of 2-phenylaniline cyclopalladated complexes

Reaction of the dinuclear complex [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl]₂ (1) with ligands (L = 4-picoline, sym-collidine) gave the six-membered palladacycles [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (2). The complex 1 reacted with AgX (X = CF₃SO₃, BF₄) and bidentate ligands [L–L = phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), bipy(2,2′-bipyridine) and dppp (bis(diphenylphosphino)propane)] giving the mononuclear orthopalladated complexes [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}(L–L)] (3) [L–L = phen, dppe, bipy and dppp]. These compounds were characterized by physico-chemical methods, and the structure of [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (L = sym-collidine) was determined by single-crystal X-ray analysis.     

Synthesis and structural characterization of ruthenium complexes with 1-aryl-imidazole-2-thione

Treatment of [RuCl₂(PPh₃)₃] with 2 equiv. Himt^MPh (Himt^MPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ ²-S,N-imt^MPh)₂(PPh₃)₂] (1), while interaction of [RuCl₂(PPh₃)₃] and 2 equiv. Himt^MPh in tetrahydrofuran (THF) without base gave [RuCl₂(κ ¹-S-Himt^MPh)₂(PPh₃)₂] (2). Treatment of [RuHCl(CO)(PPh₃)₃] with 1 equiv. Himt^MPh in THF gave [RuHCl(κ ¹-S-Himt^MPh)(CO)(PPh₃)₂] (3), whereas reaction of [RuHCl(CO)(PPh₃)₃] with 1 equiv. of the deprotonated [imt^MPh]^? or [imt^NPh]^? (imt^NPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ ²-S,N-imt^RPh)(CO)(PPh₃)₂] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ ²-S,N-imt^MPh)(CO)(PPh₃)₂] (5a) and [RuCl(κ ²-S,N-imt^NPh)(CO)(PPh₃)₂] (5b), respectively, in refluxing CHCl₃ by chloride substitution of the RuH. Photolysis of 5a in CHCl₃ at room temperature afforded an oxidized product [RuCl₂(κ ²-S,N-imt^MPh)(PPh₃)₂] (6). Reaction of 6 with excess [imt^MPh]^? afforded 1. The molecular structures of 1·EtOH, 3·C₆H₁₄, 4b·0.25CH₃COCH₃, and 6·2CH₂Cl₂ have been determined by single-crystal X-ray crystallography.     

Syntheses,structural characterization,and thermal behaviour of metal complexes with 3-aminopyridine as co-ligands

Transition Metal Chemistry - Six mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-{[M(μ2-3-ampy)(H2O)4]SO4·H2O} (M=Ni (1) and Co (2)),...     

Synthesis and structural characterization of mono- and dinuclear NiII and PdII complexes derived from tetradentate 1,7-bis-(pyridin-2-yl)-2,6-diaza-1,6-heptadiene

The reaction of Schiff base 1,7-bis-(pyridin-2-yl)-2,6-diaza-1,6-heptadiene (L) with either NiCl₂·6H₂O or [Pd^IICl₂(CH₃CN)₂]/Na[BF₄] in 1?:?1 stoichiometry yielded mononuclear ionic complexes, trans-[Ni^II(L)(H₂O)₂]Cl₂·3H₂O (1·3H₂O) and [Pd^II(L)][BF₄]₂ (2), respectively; the reaction of L with [Pd^IICl₂(CH₃CN)₂] in 1?:?2 ratio yielded dinuclear cis-[Pd^II ₂(μ-L)Cl₄] (3). Complexes 1–3 were characterized by vibrational spectroscopy and X-ray diffraction; diamagnetic 2 and 3 were also characterized by NMR in solution. The molecular structures of 1 and 2 displayed tetradentate coordination of L with formation of two five-membered and one six-membered chelate rings for both complexes. In 3, L showed bidentate coordination mode for each pyridylimine toward Pd^II. Complex 1 has distorted octahedral geometry around Ni^II and an extended hydrogen-bond network; distorted square planar geometry around Pd^II in 2 and 3 was observed.     

Synthesis and structure of the PdII complex with 3,3-dinitropropylamine

The reaction of 3,3-dinitropropylamine with PdCl₂ gave the previously unknown complex, bis(3,3-dinitropropylaminato-N,C ³)palladium(II). The structure of the complex was established by X-ray diffraction analysis. Translated fromIzvestiy Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1704–1705, September, 1997.     

Synthesis and characterization of complexes of organotin(IV) with 2-thiazoline-2-thione

The reaction of 2-thiazoline-2-thione (TZDSH) with SnR₂Cl₂ (R=Ph 1, Me 2, Bu 3) in dry ethanol in the presence of sodium ethoxide leads to [SnR₂(C₃H₄NS₂)₂] (1, 2, and 3), respectively. Reaction between TZDSH and SnPh₂Cl₂ in dichloromethane and dry ethanol in an inert atmosphere produces [SnPh₂Cl₂(C₃H₅NS₂)₂] (4). The yields of the products were over 80%. These new complexes have been characterized by IR, UV-Vis, multinuclear (¹H, ¹³C, and ¹¹⁹Sn) NMR spectroscopy, and mass spectrometry, as well as elemental analysis.     

EPR of complexes of divalent copper ions with organophosphorus derivatives of 2-aminopyridine

The complexation of copper(II) ion with organophosphorus derivatives of 2-aminopyridine was studied with EPR. It was found that, compared with 2-aminopyridine, the presence of a P-N bond in its derivatives substantially changes the character of the coordination of the ligand with respect to divalent copper, which includes an aminic nitrogen atom in the coordination sphere of the metal, and results in the formation of a four-membered chelate ring. The parameters of the EPR spectra and evaluations of the stability constants are given.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2756–2763, December, 1990.     

Synthesis and characterization of rhodium complexes with phosphine-stabilized germylenes

The reaction of phosphine-stabilized germylenes (1a,b) with dimer complex [Rh(2)(μ-Cl)(2)(COD)(2)] leads to the corresponding phosphine-germylene-Rh(I) complexes (2a,b). Interestingly, the stability of these complexes depends strongly on the nature of the substituent of the germylene fragment. Indeed, the complex (2a) with the chloro-germylene ligand isomerizes into a metallacycle rhodium complex (3a) via germylene insertion into the Rh-Cl bond, while the complex with the phenyl-substituted germylene (2b) was isolated and represents the first stable Rh(I)-germylene complex with a Rh-Cl bond.     

Synthesis and characterization of new complexes of some divalent transition metals with 2-acetyl-pyridyl-isonicotinoylhydrazone

Ten new mononuclear complexes having general formulae [ML₂](ClO₄)₂, M = Cu(II), Co(II), Ni(II), Mn(II) and Zn(II), [ML₂](SO₄), M = Co(II), Ni(II) and [ML₂(H₂O)₂](SO₄), M = Cu(II), Mn(II) and Zn(II), L = 2-acetyl-pyridyl-isonicotinoylhydrazone have been synthesized and characterized based on elemental analyses, IR spectroscopy, UV–Vis–NIR, EPR, as well as thermal analysis and determination of molar conductivity and magnetic moments. The structures of [CoL₂](ClO₄)₂ are accomplished by single crystal X-ray diffraction. The coordination sphere is formed by two N, N, O tridentates 2-acetyl-pyridyl-isonicotinoylhydrazone ligands, or by two N, O bidentate 2-acetyl-pyridyl-isonicotinoylhydrazone and two water molecules. Biological activity studies reveal a moderate activity of complexes against gram-negative and gram-positive bacteria.     

Synthesis,characterization and magnetic properties of mixed-valence iron complexes with 2-pyridyl oximes

Abstract

Two new mixed-valence iron complexes with 2-pyridyl oximes, [Fe(mpko)₃Fe(H₂O)₂(NO₃)](NO₃)·2H₂O (1) (mpko^? = methyl(2-pyridyl)ketone oximate) and [{Fe(dpko)₃}₂Fe](ClO₄)·4H₂O (2) (dpko^? = bis(2-pyridyl)ketone oximate), have been prepared by reaction of Fe^III with mpkoH in methanol (1) and Fe^II with dpkoH in methanol/water (2). Dinuclear Fe^II(low-spin)Fe^III(high-spin) and trinuclear Fe^II(low-spin)Fe^III(high-spin)Fe^II(low-spin) cations are present in the crystal structure of 1 and 2, respectively. Intermolecular hydrogen bonds in 1 lead to weak antiferromagnetic interactions between pairs of neighboring Fe^III centers, which allows observation of single-ion zero-field splitting effects.     

Synthesis and characterization of some octahedral transition metal complexes with phenyl-2-picolylketone thiosemicarbazone

Summary A series of transition metal complexes with phenyl-2-picolylketone-thiosemicarbazone, LH, of the general formula [ML₂]Cl_nmH₂O, (M=Cr³⁺, Mn²⁺, Fe²⁺, Rh³⁺, Ir³⁺ or Ru³⁺; n=0 or 1 and m=1,2 or 3) have been prepared and characterized. Magnetic and spectral (electronic and vibrational) data are commensurate with an octahedral ligand field for all complexes. The variable temperature magnetic moment shows that the iron(II) complex exists in a temperature-dependent high-spinlow-spin equilibrium. The far i.r. spectra show that the strength of the M–S bond follows the order: Mn²⁺ 2+3+3+3+3+. The various ligand field parameters, Dq, B' and are calculated.     

Synthesis,characterization and structure of oxorhenium(V) complexes with 2-methylmercaptobenzamide

The neutral, mononuclear complex [ReO(mta)₂Cl] (1) [Hmta?=?2-(methylmercapto)aniline] was prepared by reaction of trans-[ReOCl₃(PPh₃)₂] with a twofold molar excess of Hmta in methanol. The oxo-bridged dimer (μ-O)[ReO(mta)₂]₂ (2) was synthesized by reacting [ReOCl₃(PPh₃)₂] with a twofold excess of Hmta in a 9?:?1 acetone/water mixture. The compounds were characterized by spectroscopy and complex 1 also by X-ray crystallography. Complex 1 has a distorted octahedral geometry with the chloride coordinated trans to the oxo group, and with the chelating ligands in the equatorial plane in a cis-N cis-S configuration.     

Synthesis and characterization of calcium complexes containing eta 2-pyrazolato ligands

Treatment of calcium bromide with 3,5-di-tert-butylpyrazolatopotassium (2 equiv) in tetrahydrofuran afforded Ca(tBu2pz)2(THF)2 (69%). The reaction of this compound with pyridine (3 equiv), tetramethylethylenediamine (TMEDA, 1 equiv), N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA, 1 equiv), triglyme (1 equiv), and tetraglyme (1 equiv) yielded Ca(tBu2pz)2(py)3 (51%), Ca(tBu2pz)2(TMEDA) (74%), Ca(tBu2pz)2(PMDETA) (50%), Ca(tBu2pz)2(triglyme) (73%), and Ca(tBu2pz)2(tetraglyme) (57%), respectively. Treatment of the tetrahydrofuran adduct of Ca(Me2pz)2, generated in situ, with PMDETA (1 equiv), triglyme (1 equiv), and tetraglyme (1 equiv) afforded Ca(Me2pz)2(PMDETA) (65%), Ca(Me2pz)2(triglyme) (54%), and Ca(Me2pz)2(tetraglyme) (40%), respectively. The X-ray crystal structures of Ca(tBu2pz)2(py)3, Ca(tBu2pz)2(TMEDA), Ca(tBu2pz)2(PMDETA), Ca(tBu2pz)2(triglyme), and Ca(Me2pz)2(PMDETA) revealed six-, seven-, or eight-coordinate calcium centers with eta 2-pyrazolato ligands. Ca(tBu2pz)2(triglyme) sublimes at 160 degrees C (0.1 mmHg). The potential utility of these complexes as source compounds for chemical vapor deposition processes is discussed.     

Synthesis, characterization and ethylene reactivity of 2-diphenylphosphanylbenzamido nickel complexes

Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition of NiCl(eta3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C6F5)3 to the resulting products furnishes eta3-benzyl zwitterionic nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate eta1-benzyl nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray crystallography. When ethylene is added to the eta3-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, approximately 1300000) with excellent activity (up to 5200 kg mol-1 h-1 at 100 psi gauge).     

Synthesis and characterization of diorganohydrazido(2-) tungsten complexes

Diorganohydrazido(2-) complexes of tungsten (L)Cl4W(NNR2) [R2=Me2, Ph2, -(CH2)5-; L=CH3CN, pyridine] were synthesized by reacting the corresponding 1,1-diorganohydrazine with WCl6, followed by reaction with acetonitrile or pyridine. Crystallographic structure determination of (CH3CN)Cl4W(NNMe2) and (CH3CN)Cl4W(NNPh2) allows a comparison of the structural features of the diorganohydrazido(2-) functionality with varying substituents. Mass spectrometry, thermogravimetric analysis, and preliminary chemical vapor deposition experiments were performed to determine the viability of these complexes as single-source precursors for deposition of WNx and WNxCy films.