Synthesis of N'-[4'-Benzo(15-Crown-5)]-4-Tolylaminoglyoxime and N'-[4'-Benzo(15-Crown-5)]-4-Chlorophenylaminoglyoxime and Their Complexes with Copper (II), Nickel (II) and Cobalt (II)

N'-[4'-benzo(15-crown-5)]-4-tolylaminoglyoxime (H₂L¹),the sodium chloride salt of H₂L¹ (H₂L¹...NaCl),N'-[4'-benzo(15-crown-5)]-4-chlorophenylaminoglyoxime(H₂L²) and the sodium chloride salt of H₂L² (H₂L²...NaCl)have been prepared from p-chlorophenylchloroglyoxime,p-tolylchloroglyoxime, 4'-aminobenzo[15-crown-5] and sodiumbicarbonate or sodium bicarbonate and sodium chloride. Nickel (II),cobalt (II) and copper (II) complexes of H₂L and H₂L...NaClhave a metal-ligand ratio of 1 : 2 and the ligand coordinatesthrough the two N atoms, as do most of the vic-dioximes. Their IR spectra and elemental analyses are given, together with¹H NMR spectra of the ligands.     

Some new unsymmetrical diimino tetradentate schiff base derived from 3,4-Diaminobenzophenone: Synthesis, characterization and the formation constant of Ni(II) and Cu(II) complexes

Some new unsymmetrical diimino tetradentate Schiff bases derived from 3,4-diaminobenzophenone, (N-salicyliden-N′-5- OMe.salycyliden)-3,4-diaminobenzophenone (H₂sal-5-OMe.sal.dabp) (H₂L¹), (H₂sal-5-Br.sal.dabp) (H₂L²), (H₂sal-5-Cl.sal.dabp) (H₂L³) and (H₂sal-5-NO₂.sal.dabp) (H₂L⁴) and their Ni(II) and Cu(II) complexes were synthesized and characterized by elemental analysis, IR, ¹H NMR, UV-Vis spectra and mass spectra. The thermodynamic formation constants of the complexes were determined spectrophotometrically at constant ionic strength (0.1 M NaClO₄) at 25 °C in DMF and their free energies of formation were calculated at 25 °C.     

Reactions of 1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with diphenylchlorophosphane and methyl iodide

1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1, reacts with diphenylchlorophosphane to yield 1,1,3,3-tetrakis(dimethylamino)-4-diphenylphosphanyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium chloride, 2, or, depending on the reaction conditions, the isomer compound 3. The cation of 2 is deprotonated by LiN[Si(CH₃)₃]₂ to give the diphenylphosphanyl-substituted derivative of 1, i.e., compound 4. Methyl iodide adds to 1 to form 1,1,3,3-tetrakis(dimethylamino)-4-methyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium iodide, 6. Deprotonation of 6 with n-butyllithium leads to the monomethyl derivative of 1, i.e., compound 7. Physical properties, NMR spectra, and mass spectra of compounds 2–4, 6, and 7 are described. The results of the X-ray structural analysis of 6 are reported and discussed. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of cobalt(II) and copper(II) complexes with 5-amino-3,4-dimethylisoxazole

Summary Complexes of cobalt(II) and copper(II) with 5-amino-3,4-dimethylisoxazole (5-ADI) have been prepared and studied by means of magnetic susceptibility measurements, near and far i.r. spectra, electronic spectroscopy and, when possible, conductivity measurements. The 5-ADI generally behaves as bridging (N_ring-, O- or N_ring-, -NH₂) ligand. All the complexes have an octahedral sterochemistry, except Co(5-ADI)₂X₂ (X = Cl, Br), Co₂(5-ADI)₇I₄ which are tetrahedral and Cu(5-ADI)₂ (ClO₄)₂ · 4 H₂O which is square planar.     

用密度泛函理论研究一种新型有机硅化合物异构体的振动光谱

在B3LYP/6-31＋G(d)的水平上, 对两种含有手性Si原子的新型有机硅单体Si₂(CH₃)₂H₂N₂(C₂H₅)₄和Si₄(CH₃)₄H₄N₂(C₆H₅)₂的几种异构体进行了研究, 在全参量几何构型优化的基础上, 进行了简谐振动频率计算, 同时对所研究的体系进行了热力学性质和低能激发态的含时密度泛函理论(TDDFT)计算. 理论计算表明, 构象异构体之间的红外光谱差异不大, 热力学和低能激发态性质也相似; 顺/反结构相似的异构体之间红外光谱差异不大, 但热力学和低能激发态性质却呈现差异; 旋光异构体或顺/反结构相差较大的异构体之间, 红外光谱和热力学及低能激发态性质有明显的差异. 从理论上解释了实验红外光谱中Si—H振动峰的裂分是由异构体的存在所致, 并找到裂分峰所对应的异构结构. Si—H键振动频率与其键长相关.     

X-Ray Photoelectron Study of Thorium Silicate ThSiO4 · nH2O and Uranium Silicate USiO4·nH2O

The naturally occurring compounds of thorium ThSiO₄, ThSiO₄· nH₂O, and (Th, Fe)SiO₄ and uranium USiO₄· nH₂O have been studied by X-ray photoelectron spectroscopy in the range of electron binding energies from 0 to 1200 eV. The oxidation state of Th in the natural compounds is close to that in Th(OH)₄; for uranium, it is similar to that in UO₂. Based on the structure of the low-energy electron spectra it is assumed that the electrons of the filled Th6p- and O2s-atomic orbitals take an active part in chemical bonding. Fine structure was observed in the Th(U)6s-, 5d-, 5p-, 4f-, 4d-, and 4p _3/2 electron spectra of all substances under study. Mechanisms of fine structure formation are discussed and the fine structure parameters are correlated with the physicochemical properties of the compounds.     

Ion–molecule reactions of [ketene]+˙ as a diagnostic probe for distinguishing isomeric alkenes,alkynes and dienes: A study of the C4H8 and C5H8 isomeric hydrocarbons

The gas-phase ion–molecular reactions of [ketene]^+˙ with a number of isomeric alkenes, alkynes and dienes were studied by using tandem mass spectrometry. Ketene was reacted with C₄H₈ (but-1- and ?2-ene and 2-methylpropene) and C₅H₈ unsaturated hydrocarbons (isoprene, penta-1,3- and ?1,4-diene, pent-1- and ?2-yne, cyclopentene and methylenecyclobutane) in a high-pressure chemical ionization source of a tandem mass spectrometer. The collisionally stabilized ion–molecule adducts were analyzed by use of collisionally activated dissociation (CAD) spectra. The three C₄H₈ alkenes were distinguishable on the basis of the distinct CAD spectra of their adducts with ketene. Similarly, the CAD data for the corresponding adducts derived from the C₅H₈ hydrocarbons point to different structures for the C₅H₈ compounds.     

1,1,3,3,5,5-Hexakis(dimethylamino)-λ5-[1,3,5]triphosphinin – Darstellung,Kristallstruktur und NMR-Daten

1,1,3,3,5,5-Hexakis(dimethylamino)-λ⁵-[1,3,5]triphosphinine – Synthesis, Crystal Structure, and NMR Data Preparation of 1,1,3,3,5,5-hexakis(dimethylamino)-λ⁵-[1,3,5]triphosphinine ( 4 ) and the path of its formation from methyl-bis(dimethylamino)difluorophosphorane ( 1 ) and n-butyllithium are described. The chemical behaviour of compounds of type [R₂P=CH–]_n is compared with that of the isoelectronic dichlorophosphazenes [Cl₂P=N–]_n. The structure of 4 is eludicated by n.m.r. spectra and X-ray structural analysis.     

Theoretical studies on the spectroscopic properties and the substituent effects of pyridyl triazole Os(II) complexes

To explore the spectroscopic properties of pyridyl triazole Os(II) complexes and how the substituent effects affect the spectroscopic properties of [Os(ptz)₂L₂] (L=PH₃; ptzH=(2-pyridyl)-1,2,4-triazole) (1), [Os(bptz)₂L₂] (bptzH=3-tert-butyl-5-(2-pyridyl)-1,2,4-triazole) (2), [Os(fptz)₂L₂] (fptzH=3-(trifluoreomethyl)-5-(2-pyridyl)-1,2,4-triazole) (3), and [Os(fbtz)₂L₂] (fbtzH=3-(trifluoreomethyl)-5-(4-tert-butyl- 2-pyridyl)-1,2, 4-triazole) (4), the density functional theory (DFT) method at the B3LYP level was used to optimize the geometrical structures in the ground and excited state. The absorption and emission properties of the dichloromethane solution were predicted at the time-dependent density functional theory (TD-DFT, B3LYP) level associated with the PCM solvent effect model, the transitions characters of them were assigned. Important correlations between substituent effects and emission spectra and the quantum yield have been obtained by comparing and analyzing the calculated results.     

Synthesis and structure of tetracoordinated nickel(II) complexes of deprotonated chelated aminoazo ligands: X-ray crystal structure of bis[1-isopropyl-3-methyl-4-(4-methylphenylazo)-5-(4-methoxyphenylamidato)pyrazole] nickel(II)

Summary Tetracoordinate nickel(II) complexes NiL₂ derived from the deprotonated forms of aminoazoligands HL were prepared and investigated by spectroscopy and magnetic susceptibility measurements. The magnetic moments, which lie in the 3.1–3.6 B.M. range correspond to the occurrence both in solution and in the solid state of the high spin (S = 1) form and a tetrahedral configuration at the metal centre. The u.v. spectra exhibit three ligand field bands at 1020–1280 nm characteristic of high spin nickel(II) complexes. The large isotropic chemical shifts found in the ¹H n.m.r. spectra are consistent with partial delocalization of unpaired electron spin density to the ligand HOMO. The X-ray single crystal structure of NiL ₂ ⁴ [L⁴= 1-isopropyl-3-methyl-4-(4-methylphenylazo)-5-(4-methoxyphenylamino)-pyrazole] reveals that the metal is coordinated by four nitrogen atoms in tetrahedral configuration with an angle of 90° between the N(1)NiN(2) and N(6)NiN(7) planes belonging to the different almost planar metallocycles. The rates of RS interconversion of the tetrahedral configuration for NiL ₂ ⁴ and NiL ₂ ⁵ [L⁵ = 1-isopropyl-3-methyl-4-phenylazo-d ₅-5-(4-methoxyphenylamino)pyrazole] are slow on the n.m.r. timescale. In contrast to NiL ₂ ¹ -Ni ₂ ⁶ , NiL ₂ ⁷ ], which contains coordinated NH-groups instead of NAr-groups, is planar.     

Synthesis,spectral, thermal and crystallographic investigations on oxovanadium(IV) and manganese(III) complexes derived from heterocyclic β-diketone and 2-amino ethanol

Novel mononuclear oxovanadium(IV) and manganese(III) complexes [VO(L¹)₂·H₂O] (1); [VO(L²)₂·H₂O] (2); [VO(L³)₂·H₂O] (3); [Mn(L¹)₂]ClO₄·H₂O (4); [Mn(L²)₂] ClO₄·H₂O (5); [Mn(L³)₂]ClO₄·H₂O (6) were prepared by condensation of 1 mol of VOSO₄·5H₂O or Mn(OAc)₃· 2H₂O with 2 mol of ligand HL¹, HL² or HL³ (where HL¹ = 4-[(2-hydroxy-ethylamino)-methylene]-5-methyl-2- phenyl-2,4-dihydro-pyrazol-3-one; HL²=4-[(2-hydroxy-ethylamino)-methylene]-5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-one; HL³=4-{4-[(2-hydroxy-ethyl-amino)-methyl]-3-methyl-5-oxo-4,5-dihydropyrazol-1-yl} benzene sulfonic acid). The resulting complexes were characterized by elemental analyses, molar conductance, magnetic and decomposition temperature measurements, electron spin resonance, FAB mass, IR and electronic spectral studies. From TGA, DTA and DSC, the thermal behaviour and degradation kinetic were studied. Electronic spectra and magnetic susceptibility measurements indicate distorted octahedral stereochemistry of oxovanadium(IV) complexes and regular octahedral stereochemistry of manganese(III) complexes. Hamiltonian and bonding parameters found from ESR spectra indicate the metal ligand bonding is partial covalent. The X-ray single crystal determination of one of the representative ligand was carried out which suggests existence of amine-one tautomeric form in the solid state. The ¹H-NMR spectra support the existence of imine-ol form in solution state. The LC-MS studies sustain the¹H-NMR result. The electronic structure of the same representative ligand was optimized using 6-311G basis set at HF level ab initio studies to predict the coordinating atoms of the ligand.     

Vibrational spectra and normal coordinate analysis of isotactic poly(alkyl ethylene)s. I. Modification I of poly(ethyl ethylene) and its deuterated derivatives

A new calculation of the vibrational frequencies of poly(ethy1 ethylene) based on the actual molecular geometry was performed. The calculation takes into account new experimental data such far-infrared spectra and Raman spectra of the stretched polymer, infrared spectra of poly(ethyl ethylene)-(2,2;d₂) (P-4-1-d₂) and poly(ethyl ethylene)-(3,3,4,4;d₄) (P-4-1-d₄), and Raman spectra of poly(ethyl ethylene)-(1,3,3;d₃) and poly(ethyl ethylene)-(3,3,4,4;d₄). Refinement produced a set of force constants; it is also applicable to poly(propyl ethylene).     

Models of finely dispersed MgO and V<Subscript>2</Subscript>O<Subscript>5</Subscript> on silica. Theoretical analysis of optical properties using TDDFT

The results of Density Functional Theory (DFT) calculations on optical properties of vanadium complexes VOCl₃, VOCl₄ ^-, VOCl₅ ^2-, as well as the VO₄ ^3- ion, are presented. The spectra of excited states in the range 25000-60000 cm^-1 have been analyzed using the time-dependent DFT method (TDDFT). Spectroscopic features of structural defects (low-coordinated (LC) oxygen ions), as well as surface point defects (F⁺ and F sites) in MgO, have been studied within the cluster approach. The charge-transfer spectra and frequencies of normal vibrations for a number of active site models of finely dispersed oxides MgO and V₂O₅ on silica have been calculated. Comparison of the obtained results with experimental electronic diffuse reflectance spectra and fundamental frequencies confirms a hypothesis about the structure of active centers of finely dispersed oxide V₂O₅ on silica as monomeric forms, (O=V-O _n ).     

Chelate von Chinolin-8-ol — Derivaten. XI. Eigenschaften und Struktur von Nickelchelaten alkyl-substituierter Chinolin-8-ole bzw. Chinolin-8-thiole

Reactions of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete with N? H and P? H Acidic Compounds 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with aniline to give by opening of the ring 2,2,4,4-tetrakis(dimethylamino)-1-phenyl-1,2λ⁵,4λ⁵-azadiphosphapenta-1,3-diene, 2 , with p-CN? C₆F₄? NH₂ the product is 1-(4-cyano-2,3,5,6-tetrafluorophenyl)-2,2,4,4-tetrakis(dimethylamino)-1,2λ⁵,4λ⁵-azadiphosphapenta-1,3-diene, 3 . t-Butylamine or diethylamine do not react with 1 . Mesitylphosphane opens the ring system 1 forming by reduction of one phosphorus atom {[bis(dimethylamino)phosphanyl]methylidene}bis(dimethylamino)methylphosphorane, 4 . The same product 4 is obtained by reaction with phenylphosphane. The reaction products 2–4 are characterized by their nmr, mass, and ir spectra. Their way of formation is discussed. In 4 a ⁵J(PH), in 3 a ⁷J(CF) long range coupling constant could be identified.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von [(C5H5N)2CH2][PtCl5(SCN)] und cis-[(C5H5N)2CH2][PtCl4(SCN)2]

Preparation, Spectroscopic Characterization, and Crystal Structures of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] and cis -[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] By treatment of [PtCl₆]^2– with SCN^– in aqueous solution a mixture of chlorothiocyanatoplatinates(IV) is formed, from which [PtCl₅(SCN)]^2– and cis-[PtCl₄(SCN)₂]^2– have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations on single crystals of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] ( 1 ) (tetragonal, space group P 4₃, a = 7.687(1), c = 29.698(4), Z = 4) and cis-[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] ( 2 ) (monoclinic, space group P 2₁/n, a = 11.2467(9), b = 15.0445(10), c = 11.3179(13), β = 92.840(9)°, Z = 4) show, that the thiocyanate groups are coordinated via S atoms with average Pt–S distances of 2.339 Å and Pt–S–C angles of 104.7° up to 107.1°. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra have been assigned by normal coordinate analyses. The valence force constants of the S–Pt–Cl˙ axes are f_d(PtS) = 1.81 ( 1 ) and 1.87 ( 2 ), f_d(PtCl ^× ) = 1.77 ( 1 ) and 1.81 ( 2 ), of the Cl–Pt–Cl axes are f_d(PtCl) = 1.93 ( 1 ) and 1.90 mdyn/Å ( 2 ). The ¹⁹⁵Pt NMR spectra from dichlormethane solutions exhibit each one sharp signal at 3975.6 ( 1 ) and 3231.6 ppm ( 2 ), respectively.     

Vanadaphospha-alkanes and -cycloalkanes prepared by photoreaction of carbonyl-vanadium compounds with tetraphenyldiphosphines

Reaction between Ph₂PPPh₂ and [Et₄N] [V(CO)₆] yields cis-[Et₄N]₂-[(μ-Ph₂PPPh₂)₂{V(CO)₄}₂], which may have a cyclic structure, and [Et₄N]₂-[(μ-Ph₂PPPh₂){V(CO)₅}₂]. An “open-chain”, monometallic species [η⁵-CpV(CO)₃-Ph₂PPPh₂] is formed with [η⁵-CpV(CO)₄]. Proposed structures are based on IR, ³¹P, and ⁵¹V NMR spectra.     

三价轻希土—PMBP—路易斯碱三元配合物的合成及其性质的研究

合成了1—苯基—3—甲基—4—苯甲酰基—吡唑啉酮—5(PMBP)和路易斯碱的三价轻希土三元配合物LnA_3·L(A=Pmbp~-;L=C_2H_5OH时,Ln=La、Pr、Sm、对Gd为GdA_3·(C_2H_5OH)_(0·25);L=Phen(邻菲罗啉)时,Ln=Pr-Gd,L=TBPO(三丁基氧化膦)时,Ln=La、Pr—Gd)。测定了它们的摩尔电导值、热谱、红外光谱、可见—紫外光谱、荧光光谱和质子核磁共振谱。观察到热稳定性次序为LnA_3·Phen>LnA_3·TBPO。从同类型配合物系列的热效应值、LnA_3·Phen型配合物的合成难易程度及其紫外最大吸收波长的移动可观察到镧系收缩现象。     

Anionen-Massenspektroskopie von Naturstoffen. VI—Anionen-Massenspektroskopische Untersuchungen ausgewählter Gibberellin-Verbindungen

The electron attachment mass spectra (2-4 eV) of the gibberellins A₁, A₃, A₄, A₅, A₇, A₈, A₉, 3-epi-GA₁ and 3-epi-GA₃, as well as 1β-hydrxy-GA₁, are discussed and compared with the respective cation mass spectra.     

Hydroxylamido(1-)-O,N-Komplexe des Molybdäns(VI) mit terminalen Oxo-, Sulfido- und Selenido-Liganden Die Kristallstrukturen von [MoO2(C5H10NO)2] und von [MoS2(C5H10NO)2]

Hydroxylamido(1-)-O,N Complexes of Molybdenum(VI) Containing Terminal Oxo, Sulfido, and Selenido Ligands. Crystal Structures of [MoO₂(C₅H₁₀NO)₂] and of [MoS₂(C₅H₁₀NO)₂] Molecular complexes of cis-dioxo-bis(hydroxylamido(1-)-O,N)molybdenum(VI) containing O,N-coordinated, N,N-substituted hydroxylamine ligands react with H₂S in toluene substituting one or both terminal oxo groups yielding cis-oxosulfido- and cis-disulfido-bis (hydroxylamido(1-)-O,N) molybdenum complexes, respectively. With H₂Se the corresponding cis-oxoselenido complexes are formed. The crystal structures of the two title compounds containing piperidine-N-oxide as ligands are described: The cis-disulfido complex crystallizes tetragonal in the space group D—I 4 2 m with four formula units per unit cell; the corresponding cis-dioxo complex crystallizes orthorhombic (D—P 2₁2₁2₁; Z = 4). The ¹H—nmr spectra and the UV-visible absorption spectra are reported.     

Unusual template condensation of benzophenone thiosemicarbazones and salicylaldehydes with nickel(II)

Reactions of 5-R-2-hydroxybenzophenone S-methylthiosemicarbazones (R: H, Br, Cl) and 2-hydroxy-benzaldehydes in the presence of NiCl₂ yielded template complexes by chelating with two of the ligands in the monoanionic form. The N₄O₂ complexes of the thiosemicarbazones show distorted-octahedral geometry around nickel(II). The compounds were characterized by elemental analysis, conductivity and magnetic measurements, UV-Vis, IR, ¹H-NMR, and mass spectra. Crystal structure of bis-N¹-(2-hydroxy-5-bromo-phenyl)(phenyl)methylene-N⁴-(2-hydroxy-phenyl)methylene-S-methyl-thiosemicarbazidato-Ni(II) was determined by single-crystal X-ray diffraction.