Synthesis and some properties of planar 4-diphenylphosphino-1,3,2-dioxaborinanes

Fused 1,3,2-dioxaborinanes, derivatives of 4-diphenylphosphino- and 4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrenes, and their complexes with amines have been synthesized. According to X-ray diffraction data, the complex of 2-phenyl-4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrene with butylamine exists as a dimer due to the formation of intermolecular hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1655, September, 1994.The present work was financially supported by the International Science Foundation (grant No. RHBOOO).     

Strukturen neuer SeII- und TeII-Komplexe mit 2,2-Dicyanethylen-1,1-dithiolat, 2,2-Dicyanethylen-1,1-thioselenolat und 2,2-Dicyanethylen-1,1-diselenolat

Structures of New Se^II and Te^II Complexes Containing 2,2-Dicyanethylene-1,1-dithiolate, 2,2-Dicyanethylene-1,1-thioselenolate, and 2,2-Dicyanethylene-1,1-diselenolate (NBu₄)₂{Se[S₂C?C(CN)₂]₂} ( I ), (AsPh₄)₂ · {Te[SSeC?C(CN)₂]₂} ( II ), and (NBu₄)₂{Te[Se₂C?C(CN)₂]₂} ( III ) containing the bidentate chelate ligands 2,2-dicyanethylene-1,1-dithiolate i-mnt , 2,2-dicyanethylene-1,1-thioselenolate i-mnts , and 2,2-dicyanethylene-1,1-diselenolate i-mns have been prepared and characterized by X-ray structure analysis. The central units consist of [M(X? X)₂E₂]^2? (M = Se, Te; X? X = ligand; E = lone-pair) with fourfold coordinated Se^II and Te^II, respectively. The complex anions [Se(i-mnt)₂E₂]^2? as well as [Te(i-mnts)₂E₂]^2? show a trapezoide distortion with d(Se? S) = 2.276(5); 2.287(5); 2.803(5); 2.789(5) Å and d(Te? Se) = 2.611(2); 2.617(3); d(Te? S) = 2.889(5); 2.935(4) Å. In III there are centrosymmetric complex anions [Te(i-mns)₂E₂]^2? with nearly identical Te? Se-bond-lengths: 2.674(3) and 2.692(2) Å. These Te? Se bonds are elongated compared to usual Te? Se bonds.     

硼掺杂还原态氧化石墨烯催化剂的制备及其蒽催化加氢性能的研究

制备了一系列硼掺杂的还原氧化态石墨烯催化剂并应用于蒽加氢反应。结果表明，随着催化剂处理温度的升高，催化剂中有序碳结构会发生变化，硼会取代材料骨架中的碳，进而影响蒽和氢气的吸附活化。经硼改性后，催化剂对蒽加氢反应表现出了很高的加氢活性，蒽的最高转化率可达97%，深度加氢产物八氢蒽的最高选择性可达19%。     

Pyrimidino- and Proton-ionizable Pyrimidono-crown Ether Ligands: Synthesis and Preliminary Complexation Studies

Pyrimidino-crown ethers were prepared in 30-50% yields by reactingthe ditosylate derivative of the appropriate oligoethylene glycol with4-methoxy-5-methyl-2,6-pyrimidinedimethanol under basic conditions. A newmacrocyclic ligand containing a proton-ionizable pyrimidone subcyclic unitwas prepared in 88% yield by treating the appropriatepyrimidino-crown ether with 5 M NaOH in 50% (v/v) aqueous methanol.Preliminary complexation properties of some of these new compounds werestudied using various NMR spectral techniques. Good enantiomeric recognitionwas exhibited by a chiral pyrimidino-crown ether for the enantiomers of1-(-naphthyl)ethylammonium perchlorate.     

Preparation et caracterisation de complexes [cis-4,4′-dinitrodibenzo-18-couronne-6, LnCl3, 3CH3CN]

Some new complexes between thecis-4,4′-dinitrodibenzo-18-crown-6 and rare earth chlorides LnCl₃ (Ln=Nd, Gd, Yb) were synthesized in acetonitrile. Ligandcis-4,4′-dinitrodibenzo-18-crown-6 and its complexes were identified by infrared spectroscopy, X-ray diffraction and thermal analysis (TG and DTA). Acis-trans isomerisation of the complexed ligand is observed about 148°C when heating the rare earth complex.

     

High-Pressure Synthesis and Crystal Structure of B2S3

Two new high-pressure phases of binary boron-sulfur compounds, B₂S₃-II and B₂S₃-III, were synthesized at 3-6.2 GPa. A single crystal of B₂S₃-III was grown and the structure was determined (tetragonal, space group I4₁/a, a=16.086(2) Å, c=30.488(4) Å; V=7888(1) ų, Z=100, R=3.0% and R_w=2.8% for 3047 observed data [I>3.00σ(I)]. The structure of B₂S₃-III consists of two kinds of macrotetrahedra built up from 20 and 34 BS₄-tetrahedra. These macrotetrahedra connect each other to form an interpenetrating zincblende-type structure by sharing BS₄-tetrahedra at the corners of those. B₂S₃-III is anticipated having a rather disordered structure. From the UV-Vis diffuse reflectance spectrum, the optical band gap of B₂S₃-III was estimated to be 3.7 eV.     

Photophysical properties of (η2-C60)Pd(PPh3)2 complex in benzene. Picosecond and nanosecond laser photolysis

Absorption spectra of the photoexcited (²-C₆₀)Pd(PPh₃)₂ complex in benzene were obtained by picosecond and nanosecond laser photolysis. The spectra are compared with those observed for photoexcited states of fullerene C₆₀ and charge-transfer states of C₆₀ complexes with ternary amines. The relaxation kinetics of excited (²-C₆₀)Pd(PPh₃)₂ complex has three components with characteristic lifetimes ₁ = 43 ps, ₂ = 1500 ps, and ₃ = 1.17 s. The results are discussed in terms of the four-level scheme of the excited complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1163–1166, May, 1996.     

An NMR study of the rotational barriers in cobalt-stabilized carbocations: X-ray crystal structures of (η-C4Ph4)Co-(η-C5H4R), where R is CH3CO, CHO, CH(Bu)OH

Treatment of the aldehyde (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C₅H₄-CHR⁺ linkage on the NMR time-scale. These data indicate a minimum value for the barrier to rotation of 15 kcal mol⁻¹, but it is certainly much higher, indicating a considerable degree of C-C double bond character. X-ray crystal structures of 4b, 5 and also of the ketone (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-C(O)CH₃ (4a) are reported. The secondary alcohol 5 exhibits disorder in the solid state because of the presence of diastereomers as a consequence of the stereogenic center at the α-carbon and the clockwise or anticlockwise propeller orientations of the tetraphenylcyclobutadiene ligand.     

含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

Studies on some oxovanadium(IV) complexes of acyl pyrazolone analogues

A series of novel bidentate pyrazolone based Schiff base ligands were synthesized by interaction of 4-benzoyl-3-methyl-1-(4′-methylphenyl)-2-pyrazolin-5-one with various aromatic amines like aniline, o-,m-,p-chloroaniline and o-,m-,p-toluidine in a ethanolic medium. All of these ligands have been characterized on the basis of elemental analysis, IR and ¹H NMR data. The molecular geometries of five of these ligands have been determined by single crystal X-ray study. Crystallographic study reveals that these ligands exist in the amine-one tautomeric form in the solid state. NMR study also suggests the existence of the amine-one form in solution at room temperature. Ab initio calculations for representative ligand HL¹ has been carried out to know the coordination site of the ligand. Novel vanadium Schiff base complexes of these ligands with general formula [OV(L^1–7)₂(H₂O)] have been prepared by interaction of aqueous solution of vanadyl sulfate pentahydrate with DMF solution of the appropriate ligands. The resulting complexes have been characterized on the basis of elemental analysis, vanadium determination, molar conductance and magnetic measurements, thermo gravimetric analysis, infrared and electronic spectral studies. Suitable distorted octahedral structures have been proposed for these complexes.