A linear trinuclear cobalt(II) complex with 4-(2-pyridine)-1,2,4-triazole: synthesis,structure and characterization

The linear trinuclear cobalt(II) complex [Co₃(pytrz)₆(H₂O)₆](NO₃)₆ (1) with pytrz = 4-(2-pyridine)-1,2,4-triazole has been prepared and characterized. It crystallizes in the rhombohedral R-3 space group with Z = 3, a = 13.955(2), b = 13.955(2), c = 28.942(9) Å, γ = 120°, V = 4881.2(18) ų. The structure of 1 comprises the cation [Co₃(pytrz)₆(H₂O)₆]⁶⁺, in which linear trinuclear Co(II) units are bridged by six L ligands and have six aqua molecules as terminal ligands. The six free nitrates link the terminal aqua ligands through N–H ··· O hydrogen bonds with C₃ symmetry. 1 was characterized by FT-IR, electronic spectra and magnetic measurements. The variable-temperature magnetic measurements reveal weak anti-ferromagnetic interactions in 1.     

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.     

Syntheses and structures of Tetranuclear Cluster complexes of molybdenum [Mo4(μ3-S)2(μ2-S)4 X 2-(PMe3)6] (X = SH,Cl, Br,I, SCN) and [Mo4(μ3-S)2-(μ2-S)4 (dtc)2(PMe3)4] (dtc = diethyldithiocarbamate)

A molybdenum cluster complex [Mo₄(μ₃-S)₂(μ₂-S)₄)(SH)₂(PMe_{3 6}] has been synthesized by the reaction of (NH₄)₂Mo₃S₁₃ with trimethylphosphine. The cluster core is composed of four molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six tri-methylphosphine ligands are coordinated to the terminal positions. The mean oxidation stares of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo₄(μ₃-S)₂(μ₂-S)₄ X ₂(PMe₃)₆] (X=Cl, Br, I, SCN) and [Mo₄μ₃-S₂(μ₂-S)₄ (die)₂(PMe₃)₄] (dtc - diethyldithiocarbamate). In the case of the dtc complex, two terminal trimetlaylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo₄S₆ X ₂(PH₃)₄] (X= SH, Cl, and Br).     

3-(2-吡啶基)-1,2,4-三唑配体Co(II)Cu(II)和Cd(II)配合物的合成、结构及荧光性质

利用3-（2-吡啶基）-1,2,4-三唑配体（HL）和不同的金属盐设计合成了5个配合物[Co（HL）₂（H₂O）₂]（NO₃）₂（1）、[Cu₂（L）₂（NO₃）₂（H₂O）₄] （2）、[Cu₂（L）₂（AcO）₂（H₂O）₂]·6H₂O （3）、[Cu₂（L）₂（HL）₂（ClO₄）₂]·2CH₃CN （4）和[Cd₂（L）₂（HL）₂（NO₃）₂]·2H₂O （5）,并通过X射线单晶衍射、红外、元素分析、X射线粉末衍射和热重对配合物结构进行了表征。测试结果表明配合物1具有单核结构,并且可以通过氢键的相互作用形成二维超分子结构。配合物2~5为双核结构。配合物2和5可以通过氢键的相互作用形成二维超分子结构。配合物3通过氢键的相互作用形成三维超分子结构。研究了配合物中HL配体的配位模式。此外,研究了配体HL和配合物1和5的固态荧光性质及荧光寿命。     

Complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole

Novel oligonuclear complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole (L) of the composition [M₃L₁₀(H₂O)₂](NO₃)₆ (M = Co(II), Ni(II)), [Ni₃L₆(H₂O)₆]Hal₆ (Hal = Cl^?, Br^?), and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O were synthesized and studied by magnetic susceptibility, electronic and IR spectroscopy, and powder X-ray diffraction methods. All the above complexes are X-ray amorphous. Antifer-romagnetic exchange interactions between the M²⁺ ions were discovered in the [Co₃L₁₀(H₂O)₂](NO₃)₆ and [Ni₃L₁₀(H₂O)₂](NO₃)₆ complexes, whereas ferromagnetic exchange interactions were observed in the complexes [Ni₃L₆(H₂O)₆]Cl₆, [Ni₃L₆(H₂O)₆]Br₆, and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O.     

Palladium(II)-, Platin(II)-, Ruthenium(II)-, Rhodium(III)- und Iridium(III)-Komplexe von Desoxyfructosazin

Metal Complexes of Biologically Important Ligands. CIII. [1] Palladium(II), Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) Complexes of Desoxyfructosazine The reactions of the pyrazine derivative desoxyfructosazin(pz) with K₂PtCl₄ and with the chlorobridged [M(PR₃)Cl₂]₂ (M = Pd, Pt), [(η⁵-C₅Me₅)MCl₂]₂ and [(η⁶-p-Cymol)RuCl₂]₂ give the watersoluble complexes cis-Cl₂Pt(pz)₂, (R₃P)(Cl)M(pz)M(Cl)(PR₃) (M = Pd, Pt), (η⁵-C₅Me₅)(Cl)₂M(pz)M(Cl)₂(η⁵-C₅Me₅) (M = Rh, Ir), (η⁶-p-Cymol)(Cl₂)Ru(pz)Ru(Cl)₂(η⁶-p-Cymol).     

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.     

Darstellung carboxylatsubstituierter Rhenium-Gold-Metallatetrahedrane Re2(AuPPh3)2(μ-PCy2)(CO)7(η1-OC(R)O) (R = H,Me, CF3, Ph, 3,4-(OMe)2C6H3)

Synthesis of Carboxylate Substituted Rhenium Gold Metallatetrahedranes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H, Me, CF₃, Ph, 3,4-(OMe)₂C₆H₃) The reaction of the in situ prepared salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(ax-C(Ph)O)] ( 2 ) with 1,5 equivalents of monocarboxylic acid RCOOH (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e ) in tetrahydrofruan (THF) solution at 60 °C gives within 4 h under release of benzaldehyde (PhCHO) the η¹-carboxylate substituted dirhenium salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(η¹-OC(R)O)] (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e )) in almost quantitative yield. The lower the pK_a value of the respective carboxylic acid the faster the reaction proceeds. It was only in the case of CF₃COOH possible to prove the formation of the hydroxycarbene complex Re₂(μ-H)(μ-PCy₂)(CO)₇(=C(Ph)OH) ( 5 ) prior to elimination of PhCHO. The new compounds 4 a–4 e were only characterized by ³¹P NMR and ν(CO) IR spectroscopy as they are only stable in solution. They are converted with two equivalents of BF₄AuPPh₃ at 0 °C in a so-called cluster expansion reaction into the heterometallic metallatetrahedrane complexes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H ( 7 a ), Me ( 7 b ), CF₃ ( 7 c ), Ph ( 7 d ), 3,4-(OMe)₂C₆H₃ ( 7 e )) (yield 47–71% ). The expected precursor complexes of 7 a–7 e Li[Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(R)O] ( 8 ) were not detected by NMR and IR spectroscopy in the course of the reaction. Their existence was retrosynthetically proved by the reaction of 7 b with an excess of the chelating base TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-en) forming [(TBD)_xAuPPh₃][Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(Me)O] ( 8 b ) in solution. The η¹-bound carboxylate ligand in 7 a–7 e can photochemically be converted into a μ-bound ligand in Re₂(AuPPh₃)₂(μ-PCy₂)(μ-OC(R)O)(CO)₆ (R = H ( 9 a ), Me ( 9 b ), CF₃ ( 9 c ), Ph ( 9 d ), 3.4-(MeO)₂C₆H₃ ( 9 e )) under release of one equivalent CO. All isolated cluster complexes were characterized and identified by the following analytical methods: elementary analysis, NMR (¹H, ³¹P) spectroscopy, ν(CO) IR spectroscopy and in the case of 7 d and 9 b by X-ray structure analysis.     

Copper(I) and Silver(I) Complexes of 1-alkyl-2-(methyl)-4-(arylazo)imidazole. Synthesis, Spectral Studies and Electrochemistry

2-(Methyl)-4-(arylazo)imidazole (RLH) (1, 2) are new series of azoimidazoles. Upon treatment of alkylhalide in dry THF in presence of NaH has synthesised 1-alkyl-2-(methyl)-4-(arylazo)imidazole (RLR′) (3, 4). They belong to the azoimine family of N,N′-chelating ligand. They stabilize the Cu(I) oxidation state and we have synthesized [Cu(RLR′)₂](ClO₄) (5, 6). These complexes show a moderately intense visible band (500–600 nm) which has been assigned to 3d(Cu) → π*(ligand) transition. Ag(I) complexes of RLR′ (7, 8) are also very stable under ambient conditions and show weak transitions in the visible region. The Cu(I)-complexes show high potential Cu(II)/Cu(I) redox couple > 0.4 V vs Ag, AgCl/Cl⁻ reference electrode. All these complexes have been structurally characterized by ¹H NMR spectroscopic data.     

Seleniumselenium bond reactions of μ-(diselenium)bis(tricarbonyliron), an inorganic mimic of organic diselenides

μ-(Diselenium)bis(tricarbonyliron), (μ-Se₂)Fe₂(CO)₆, has been found to have reactivity typical of organic diselenides, RSeSeR. Reaction with two molar equivalents of LiBEt₃H converts (μ-Se₂)Fe₂(CO)₆ to the dianion, (μ-LiSe)₂Fe₂(CO)₆. Organolithium reagents, RLi, cleave its SeSe bond, giving (μ-LiSe)(μ-RSe)Fe₂(CO)₆. Low valent transition metal species, e.g., (Ph₃P)₂Pt, insert into the SeSe bond. (μ-Se₂)Fe₂(CO)₆ is fragmented by the action of dicobalt octacarbonyl, giving (μ₃-Se)FeCo₂(CO)₉.     

Cobalt(II) complexes with pyridine and 5-[(E)-2-(aryl)-1-diazenyl]-quinolin-8-olates: synthesis,electrochemistry and X-ray structural characterization

Abstract

Nine new cobalt(II) compounds, trans-[Co(L^PAQ)₂(Py)₂] (1), trans-[Co(L^PAQ)₂(3-MePy)₂] (2), trans-[Co(L^MeAQ)₂(Py)₂] (3), trans-[Co(L^OMeAQ)₂(Py)₂] (4), trans-[Co(L^OEtAQ)₂(Py)₂]·2(H₂O) (5), trans-[Co(L^CAQ)₂(Py)₂] (6), trans-[Co(L^BAQ)₂(Py)₂] (7), cis-[Co(L^BAQ)₂(3-MePy)₂] (8a) and trans-[Co(L^BAQ)₂(3-MePy)₂]·2(3-MePy) (8b) (primary ligand: L^XAQ?=?substituted 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olate; secondary ligands: Py?=?pyridine, 3-MePy = 3-methylpyridine), have been synthesized and characterized by elemental analysis, IR and UV-vis spectroscopy. Magnetic measurements of the cobalt compounds were performed in solution by ¹H NMR spectroscopy using the Evans’ method while their redox properties were studied by cyclic voltammetry. Single-crystal X-ray diffraction analysis of the compounds revealed their octahedral geometries and trans configuration, except for 8a, which has a cis configuration. Intermolecular noncovalent interactions were detected, π···π interactions in 5, C?–?H···π interactions in 2 and C?–?H···π edge-to-face (T-shaped) arrangements in 3, 4, 6, and 7.     

The preparation and X-ray crystal and molecular structure of (α,1,2-η-6-methylbenzyl) bis(triphenylphosphine)rhodium(I)

Reaction of [RhCl(PPh₃)₃] with [o-MeC₆H₄CH₂MgBr] affords high yields of the non-fluxional complex, [Rh(CH₂C₆H₄Me)(PPh₃)₂] which has been shown crystallographically to contain a 1-3-η-benzyl group bound through the phenyl carbon atom that is not substituted with the methyl group. Crystals of this compound are triclinic, space group P$\text{1}$, with a = 10.561(6). b = 17.705(3), c = 10.934(4) Å, α = 80.69(3), β = 116.86(4), γ = 102.30(4)° and Z = 2. The structure was solved via the heavy-atom method and refined to R = 0.032 using 5379 diffractometer data with I > 1.56(I). Attempts to prepare π-bonded xylylene complexes from this compound by reaction with base have been unsuccessful, but protonation followed by recrystallisation from acetone gives [Rh{(CH₃)₂CO}₂(PPh₃)₂]BF₄.     

Synthesis,spectroscopic characterization,X-ray structure and DFT calculations of copper(II) complex with 2-(2-pyridyl)benzimidazole

The reaction of copper(II) nitrate trihydrate and 2-(2-pyridyl)benzimidazole (pybzim) leads to [Cu(pybzim)₂(NO₃)](NO₃). The compound has been studied by IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure of the [Cu(pybzim)₂(NO₃)]⁺ cation has been calculated with the density functional theory (DFT) method. The spin-allowed doublet–doublet electronic transitions of [Cu(pybzim)₂(NO₃)]⁺ have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis.     

Azoimidazole Complexes of Manganese(II)-thiocyanate. X-ray Structures of 2-(p-tolylazo)imidazole and Bis-[1-methyl-2-(p-tolylazo)imidazole]- Di-thiocyanato-manganese(II)

The reaction of Mn(OAc)₂ · 4H₂O and 1-alkyl-2-(arylazo)imidazole [RaaiR′ where R = H (a), Me (b); R′ = Me (1/3/), Et (2/4/)] and NH₄NCS in MeOH in a 1:2:2 mole ratio afforded [Mn(RaaiR′)₂(NCS)₂] (3) and (4) complexes. They were characterized by different physicochemical methods and the structure has been confirmed by single crystal X-ray diffraction study for title compound. One of the primary ligands was also characterised by an X-ray diffraction study.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Synthesis,spectroscopic, biological,and theoretical studies of new complexes from (E)-3-(2-(5, 6- diphenyl-1,2,4- triazin-3- yl)hydrazono)butan-2- one oxime

New mononuclear Fe (III), Cu (II), Ag (I), ZrO ( IV) and UO₂(VI) complexes were synthesized by the reaction of metal ions with (E)-3-(2-(5, 6- diphenyl-1,2,4- triazin-3- yl)hydrazono)butan-2- one oxime. The structures of the metal complexes were characterized using analytical, spectral (infrared, electronic, ¹H NMR, electron spin resonance (ESR), and mass), magnetic moment, molar conductance, thermal gravimetric analysis, and powder X-ray diffraction (XRD) measurements. All complexes have octahedral geometries except the Cu (II) complex, which has square planar geometry, and the UO₂(VI) complex, in which the coordination number is seven. The ligand acts as a (neutral, monoanionic or dianionic) tridentate with N₂O coordinating sites: N-azomethine, N-triazine, and O-oxime. Fluorescence spectral studies were carried out in solid state and in dimethylformamide (DMF). The kinetic parameters of the thermal decomposition stages were calculated using Coats–Redfern equations. The morphological structures of the ligand and some complexes were determined using XRD. The molecular orbital calculations were carried out for the ligand and metal complexes using the Hyperchem 7.52 program on the basis of the PM3 level. The antimicrobial activities of the ligand and its complexes were investigated towards the microorganisms S. aureus and B. subtilis as Gram-positive bacteria, S. typhimurium and E. coli as Gram-negative bacteria, C. albicans, and A. fumigatus. The ligand and its complexes showed antitumor activity against Hep G-2 cell lines, where Cu (II) and Ag (I) complexes seem to be promising as they showed IC₅₀ values that are lower than and comparable to that of the antitumor drug doxorubicin.     

Synthesis and spectroscopic characterization of heterobimetallic (α-alkynyl)iron-cobalt hexacarbonyl complexes, μ-(1-σ, 2-3, η2-R2C-CCR′)][(CO)3Fe-Co(CO)3] and [μ-(1-σ, 2-3, η2-H2C-CCCH2OH)] [(CO)3Fe-Co(CO)2(PPh3)]

The title compounds have been prepared from reactions of Co₂(CO)₆(μ-HOR₂CC₂R′) or Co₂(CO)₆(μ-HOR₂CC₂CR₂OH) complexes with Fe(CO)₅ in acetone. In the latter set of reactions the homobimetallic butatriene compounds, Fe₂(CO)₆-(μ-R₂CCCCR₂), are also obtained. The striking feature of these reactions is the ability of Fe(CO)₅ to dehydroxylate the organic moiety and to replace a Co(CO)₃ unit forming mixed iron-cobalt derivatives. A direct interaction between the iron and the carbon atom, originally bearing the lost -OH group, is evident from the bulk of the spectroscopic data; thus the organic chain acts as an overall 5 electron donor, according to the E.A.N. formalism. The heterobimetallic compounds have been characterized by elemental analysis, mass spectrometry, IR spectroscopy and NMR studies. For the phosphine derivative FeCo(CO)₅(PPh₃)(H₂CC₂OH) a crudely refined X-ray analysis has been performed.     

以2-(1-吡唑基甲基)吡啶类化合物为配体的羰基钼、钨衍生物的合成及结构

合成了2-[1-(3-叔丁基)吡唑基甲基]吡啶(CH2(Py)(3-ButPz)),并研究了羰基钼(钨)与该配体及其类似物2-(1-吡唑基甲基)吡啶(CH2(Py)(Pz))和2-[1-(3,5-二甲基)吡唑基甲基]吡啶(CH2(Py)(3,5-Me2Pz))的反应,合成了6个含双齿螯合的2-(1-吡唑基甲基)吡啶类配体的四羰基金属衍生物CH2(Py)(3-ButPz)M(CO)4,CH2(Py)(Pz)M(CO)4和CH2(Py)(3,5-Me2Pz)M(CO)4(M=Mo或W)。当用SnCl4处理CH2(Py)(3,5-Me2Pz)M(CO)4时,Sn-Cl键对金属中心发生氧化加成得到2个杂双核金属有机化合物CH2(Py)(3,5-Me2Pz)M(CO)3(Cl)SnCl3。所有新化合物均通过了红外和核磁的表征,CH2(Py)(3-ButPz)W(CO)4和CH2(Py)(3,5-Me2Pz)W(CO)3(Cl)SnCl3的结构还得到了X-射线单晶衍射的确证。用循环伏安法测定了四羰基金属衍生物的电化学性质。     

Syntheses and structures of N-polyfluorophenyl- and N,N′-bis(polyfluorophenyl)ethane-1,2-diaminato(1- or 2-)platinum(II) complexes

The reaction of [PtX₂(L)] (X = Cl, Br, I; L = NH₂CH₂CH₂NY₂; Y = Et, Me) with thallium(I) carbonate and a polyfluorobenzene (RF) in pyridine (py) yields the platinum(II) complexes, [Pt{N(R)CH₂CH₂NY₂}X(py)] (R = C₆F₅, 4-HC₆F₄, 4-BrC₆F₄, or 4-IC₆F₄, Y = Et (1), Me (2), X = Cl, Br or I) in an improved synthesis. From the reaction of [PtCl₂(H₂NCH₂)₂)] with Tl₂CO₃ and 1,2,3,4-tetrafluorobenzene or 2-bromo-1,3,4,5-tetrafluorobenzene in py, the new complexes [Pt(NRCH₂)₂(py)₂] (3) (R = C₆H₂F₃-2,3,6 and C₆HBrF₃-2,3,5,6) have been isolated but the latter preparation also gave product(s) with a 4-bromo-2,3,5-trifluorophenyl group. From an analogous preparation in 4-ethylpyridine (etpy), [Pt(N(4-HC₆F₄)CH₂)₂(etpy)₂] (4) was obtained. The X-ray crystal structures of (3) (R = C₆HBrF₃-2,3,5,6) and (4) were determined as well as that of the previously prepared (3) (R = 4-BrC₆F₄) and a more precise structure of (3) (R = 4-HC₆F₄) has been obtained.     

Zur Charakterisierung von Eigenschaften der versteiften dreizähnigen Aminophosphanliganden N,N'-Bis(diphenylphosphino)-2,6-diaminopyridin und N,N-Bis(diphenylphosphino)-2-aminopyridin mit Metallen der Chromgruppe

Inhaltsübersicht. Edukte von Typ M(CO)₆ (M = Cr, Mo,W), N,N'-Bis(diphenylphosphino)-2,6-diaminopyridin (PNP) und Trimethylaminoxid setzen sich bei Raumtemperatur nicht zu dem bekannten Verbindungstyp mer-M(CO)₃PNP, sondern zu Verbindungen der beiden Typen M(CO)₄(PNP=O) mit zweizähnig koordinierten Liganden PNP=O und M(CO)₅(NMe₃) um. Die zu Vergleichszwecken untersuchte Oxidation eines koordinierten PNP-Liganden von mer-Mo(CO)₃(PNP) in Tetramethylbenzollösung ergibt mit Luftsauerstoff bei 180°C eine Reaktion unter Spaltung der P–N-Bindung zur cubanartigen Verbindung Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O₄ (Ausbeute 48%). In einem Glaseinschlußrohr reagiert der ambidente N,N-Bis(diphenyIphosphino)-2-nminopyridin-Ligand (NPP) mit den Hexacarbonylen M(CO)₆ in Toluollösung bei 140°C zu Verbindungen des Typs M(CO)₄(NPP) mit zweizähniger Verknüpfung des NPP-Liganden. Hierbei bilden die beiden P-Donoratome am Aminstickstoffatom einen MP₂N-Chelatvierring an Stelle des ebenfalls möglichen P, N_py-Chelatfünfrings. Der analoge Chelatvierring entsteht gleichfalls bei einer Ligandensubstitutions-reaktion zwischen Verbindungen des Zweikernkomplextyps MM′(CO)₈(μ-PPh₂)₂ (M = M′ = W; M = Mo, M′ = W) bzw. \V(CO)₄(μ-PPh₂)₂IrH(CO)(PPh₃) und NPP. Er bildet sich außerdem bei der Thermolyse von Mo(CO)₄(NPP) zu Mo₂(CO)₆(μ-PPh₂)₂(NPP). Die Identifizierung erfolgt im Falle der Verbindungen Mo(CO)₄(PNP=O), Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O_4′ Mo₂(CO)₆(μ-PPh₂)₂(NPP) und W(CO)₄(μ-PPh₂)₂IrH(CO)(NPP) durch Einkristall-Röntgenstrukturanalysen. Alle isolierten Produkte werden durch spektroskopische Messungen insbesondere ³¹P-NMR-Daten charakterisiert. Characterization of Properties of the Rigid Tridentate Chelate Ligand N,N′-Bis(diphenylphosphino)-2,6-diaminopyridine and N,N-Bis(diphenylphosphino)-2-aminopyridine with Transition Metals of the Chromium Group Hexacarbonyls M(CO)₆ (M = Cr, Mo, W), N,N′-Bis(diphenylphosphino)-2,6-diaminopyridine (PNP) and trimethylamine oxide gave products of two types M(CO)₄(PNP=O) having a bidentate ligand PNP=O and M(CO)₅(NMe₃) instead of the desired mer-M(CO)₃PNP. For the purpose of a comparison, aerial oxidation of mer-Mo(CO)₃PNP in tetramethyl benzene solution at 180°C was examined which resulted a P–N bond rupture under formation of the cubane-like product Mo₄(μ₃-O)₄(μ-Ph₂PO₂C₄O₄){yield 48%). In sealed glass tubes the ambidentate ligand N,N-bis(diphenylphosphino)-2-aminopyridine (NPP) was reacted with the hexacarbonyls M(CO)₆ in toluene solution at 140°C to products of the type M(CO)₄NPP with NPP as bidentate ligand. Under this reaction conditions the four-membered chelate ring of the type MP₂N was formed with the two P donor atoms attached to the amine N atom instead of the possible competitive five-membered chelate ring formation with a P and pyridyl nitrogen. The analogous four-membered chelate ring was formed in ligand substitution reactions between the substance NPP and each of the dinuclear coordination compounds MM′(CO)₈(μ-PPh₂)₂ (M = M′ = W, M = Mo, M′ = W) including W(CO)₄(μ-PPh₂)₂IrH(CO)(PPh₃); Mo₂(CO)6(μ-PPh₂)₂(NPP) was obtained via thermolysis of Mo(CO)₄(PNP=O). The given structural identification of the compounds Mo(CO)₄(PNP=O), Mo₄(μ₃-O)₄(μ-Ph₂PO₂)₄O₄, Mo₂(CO)₆ (μ-PPh₂)₂(NPP) and W(CO)₄(μ-PPh₂)₂IrH(CO) (NPP) was done by single-crystal X-ray analysis. All seperated products have been characterized by means of spectroscopic measurements especially ³¹P n.m.r. data.