SYNTHESIS AND CHARACTERIZATION OF BIS-[2-[[(2-ALKOXYPHENYL)IMINO]METHYL]-PHENOLATO-O,N,O]NICKEL(II)COMPLEXES AND THEIR NORBORNENE POLYMERIZATION

A series of salicylaldimines,synthesized in high yield via microwave-assisted condensation of salicylaldehyde and 2-alkoxyaniline were allowed to react with nickel chloride to form six-coordinated nickel complexes.These nickel complexes were carefully characterized,and the solid structure of la was elucidated by X-Ray diffraction.Activated with MAO,the nickel complexes showed good activity for homopolymerization of norbornene.Reaction parameters,such as the ratio of nickel precursor to MAO,monomer concentration,reaction time and the reaction temperature,as well as the nature of the ligands were found to have significant effects on the catalytic activity and some properties of the resulting polynorbornene.     

SELENOETHER COMPLEXES OF COPPER(II) ‐ SYNTHESIS,SPECTROSCOPY AND STRUCTURES

Abstract

The red-brown copper(II) diselenoether complexes, [Cu (L-L)₂][BF₄]₂ (L-L = MeSeCH₂CH₂SeMe, MeSeCH₂CH₂CH₂SeMe or PhSeCH₂CH₂SePh) have been prepared from copper(II) fluoroborate and the ligands in anhydrous dichloromethane. Some new dithioether analogues are also described. The reaction of MeSeCH₂CH₂SeMe and copper(II) fluoroborate in ethanol led to an unstable dark green substance which appeared to contain both copper(I) and copper(II) and was formulated [Cu(MeSeCH₂CH₂SeMe)₂] [BF₄]_x. The complexes were characterised by analysis, UV-visible and e.p.r. spectroscopy, and magnetic measurements, and cyclic voltammetry has been used to probe the Cu (II)/Cu(I) redox couples. The complexes are too unstable in solution to obtain crystals for an X-ray study, but structural data has been obtained for both the Cu(II) and Cu(I) complexes by copper K-edge EXAFS studies. Ditelluroethers reduce copper(II) salts to copper(I) complexes.     

TRANSITION METAL COMPLEXES WITH THIOSEMICARBAZIDE-BASED LIGANDS. PART 25. SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF CIS-DIOXO [(SALICYLALDEHYDE THIOSEMICARBAZONATO(1-))] AQUOMOLYBDENUM (VI)CHLORIDE MONOHYDRATE, [MoO2(HL)H2O]Cl·H2O

Abstract

The synthesis and crystal structure analysis of the diamagnetic complex [MoO₂(HL)H₂O]Cl·H₂O(HL = monoanion of salicylaldehyde thiosemicarbazone) are reported. The complex crystallizes in the space group P2₁/a (No. 14) with a = 11.003(1), b = 8.444(1), c = 15.364(1) Å, β = 104.96(1)°, V = 1379.1(2) ų. X-ray structure determination revealed that the complex possesses the usual cis-MoO₂ ²⁺ core and that the thiosemicarbazide ligand is present as a monoanionic tridentate donor coordinating through ONS. According to a search in the Cambridge Structural Database (state April 1994) this complex is the first in which the sixth coordination site at Mo(VI) is occupied by a water molecule forming a distorted octahedral coordination geometry together with the tridentate ligand.     

NICKEL(II) AND EUROPIUM(III) COMPLEXES OF THE AMINOPHENOL LIGAND: 2-(DIETHYLAMINO)METHYLPHENOL (N∼OH). CRYSTAL STRUCTURES OF THE Ni(N∼O)2 AND [Eu(NO3)3(HN∼O)2]2 COMPLEXES

Abstract

The first Ni(II) compounds with aminophenol ligands were synthesized by reaction of 2-diethylaminomethylphenol and 2-diethylaminomethyl-4-methylphenol (N ～ OH) with dehydrated NiCl₂ in ethanol. They were characterized as tran-square planar Ni(N ～ O)₂ complexes by NMR and IR spectroscopies, mass spectrometry, elemental analysis and X-ray structure determination. When the ligand was reacted with Eu(NO₃)₃, the new dimeric complex [Eu(NO₃)₃(HN ～ O)₂]₂ was isolated. Elemental analysis, IR, magnetic moment and X-ray diffraction indicated that in this case formally neutral aminophenol ligands, in their zwitterionic form, are attached to the metal center through the phenolato oxygen and act either as bridging or as terminal groups. Their protonated amino substituents are involved in strong N—H—O hydrogen bridging. The metal shows nine-coordination, the coordination sphere of each europium being completed by three NO₃ groups.     

CHIRAL COMPLEXES BY DIRECT SYNTHESIS OF A BIOMOLECULE AND METAL POWDERS. CRYSTAL STRUCTURES OF THE DICHLORO[(−)-SPARTEINE-N,N′]M(II) COMPLEXES (M = Cu,Zn)

Abstract

Direct synthesis of chiral complexes dichloro[(?)-sparteine-N,N′]copper(II) 2 and dichloro[(?)-sparteine-N,N′]zinc(II) 3 derived from a biomolecule-namely the natural base (?)-sparteine- and elemental metals (Cu and Zn) in a CCl₄/DMSO solvent system (DMSO = dimethylsulfoxide) is reported. The complexes were partly characterized by spectroscopic methods and their structures were fully confirmed by single-crystal x-ray analysis. A comparison between the new crystal structures of 2 and 3 and that of the free ligand (?)-sparteine displayed only slight differences on the ligand framework.     

CRYSTAL AND MOLECULAR STRUCTURES OF THE DERIVA-TIVES OF ( + )- 1K, 3K(S) , 5S-2,4,3-DIAZAPHOSPHABICYCLO-[3. 2. 1]OCTANE

<正> Compound C9H19N2OPS (1) , Mr = 234. 3, monoclinic, space group P21, a = 7. 5637(2), b = 7. 704(2), c=10. 258(1) (?) ,β = 98. 66(2)°, V = 590. 9(?)3, Z =2, Dc=1. 317g/cm3, F(000) = 252. The final R = 0. 063 and Rw = 0. 080 with unit weight for 870 observed reflections (I≥3σ(I)). Compound C10H22 N3PS(2), Mr = 247. 34, monoclinic, space group P21, a = 7. 656(1), b = 8. 248 (1), c=10.750(l)(?), β=91.31(1)°, 7 = 678.73(?)3, Z = 2, Dc=1. 21g/cm3, final R = 0. 066 and Rw = 0. 081 with unit weight for 813 observed reflections (I≥3σ (I)), F(000) = 268. Both skeletons of (1) and (2) have similar geometry, which is composed of three rings : a seven-membered ring in a boat form, a six-membered ring in a chair conformation, and a five-membered ring in envelope form. The configura-tions of the chiral phosphorus atoms are assigned as 3R for (1) and as 3S for (2).     

SYNTHESIS,CRYSTAL STRUCTURE AND DFT STUDY OF NOVEL (2S,2′S,6R,6′R)-4,4′-(6-BROMOPYRIDO[2,3-d]PYRIMIDINE-2,4-DIYL)BIS(2,6-DIMETHYLMORPHOLINE)

Journal of Structural Chemistry - (2S,2′S,6R,6′R)-4,4′-(6-Bromopyrido[2,3-d]pyrimidine-2,4-diyl)bis(2,6-dimethylmorpholine) is a novel organic intermediate having...     

SYNTHESIS AND CHARACTERIZATION OF BIS-[2-[[（2- ALKOXYPHENYL）IMINO]METHYL]-PHENOLATO-O,N,O]NICKEL（Ⅱ） COMPLEXES AND THEIR NORBORNENE POLYMERIZATION

A series of salicylaldimines, synthesized in high yield via microwave-assisted condensation of salicylaldehyde and 2-alkoxyaniline were allowed to react with nickel chloride to form six-coordinated nickel complexes. These nickel complexes were carefully characterized, and the solid structure of la was elucidated by X-Ray diffraction. Activated with MAO, the nickel complexes showed good activity for homopolymerization of norbornene. Reaction parameters, such as the ratio of nickel precursor to MAO, monomer concentration, reaction time and the reaction temperature, as well as the nature of the ligands were found to have significant effects on the catalytic activity and some properties of the resulting polynorbornene.     

SYNTHESIS AND CRYSTAL STRUCTURE OF V ^（v）O[N（CH2Ch2O）3]

<正> Reaction of ammonium metavanadate with triethanolamine in ethanol yields the title compound (2,2' , 2"-nitrilotriethoxy)oxo-vanadium (Ⅴ ). The crystal and molecular structure has been determined crystallographically. The complex V(v) O[N(CH2CH2O)3] crystallzes in the monoclinic system, space group P21, a = 7.140(1), 6 = 7.474(2), c=8.040(2) A ,β=92. 48(2)°, V=428. 7(1) A3, Mr= 213.1, Z = 2, F(000) = 220,μ= 10. 95cm-1, Dc= 1. 65gcm-3, final R= 0. 032 and Rw = 0. 034 based on 758 independant reflections with I>2σ(I). The vanadium center is in a distorted trigonal bipyramidal environment of a quadridentate chelating ligand and a terminal oxygen atom.     

SYNTHESIS AND CRYSTAL STRUCTURE OF Eu[（CH3O）2PO2]3

<正> The title complex has been synthesized and characterized by elementary analysis,FT-IR and Raman spectra. The crystal and molecular structure was determined by X-ray diffraction analysis. The crystal of this complex C6H18O12P3Eu(Mr = 527. 08) is monoclinic with space group P21/c and cell parameters a= 10. 418(2) ,b= 16. 596(6) ,c =10. 766(2) A ,β=111. 67(2)°,V=1729. 8(8) A3 and Z=4. Dimethyl phosphate an-ions coordinate with europium ions through double O-P-O bridges to form a special network of rings-linking-rings. The local coordination geometry of Eu is a slightly distorted octahedron.     

SYNTHESES,CRYSTAL STRUCTURES AND UREASE INHIBITORY ACTIVITIES OF ZnII AND NiII COMPLEXES DERIVED FROM 4,4′-DIMETHOXY-2,2′-(PROPANE-1,3- DIYLDIIMINODIMETHYLENE)DIPHENOL

Journal of Structural Chemistry - Two new zinc(II) and nickel(II) complexes, [Zn2L(μ2-η1:η1-CH3COO)(μ2-η1:η2-CH3COO)]n (1) and...     

THE CLEAVAGE REACTION OF Mo≡Mo TRIPLE BOND.SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF[CpMo(CO)_2(N,S-C9H6NS)]·O=PPh3

The reaction of[CpMo(CO)_2]_2 with 8,8'-diquinolyl disulphideC_9H_6NSSNC_9H_6 resulted in the cleavage of Mo≡Mo triple bond to give a newnononuclear complex CpMo(CO)_2(N,S-C_9H_6NS)which was refluxed with PPh_3 inTHF to form the title complex.The crystal structure of the title complexwas determined by X-ray diffraction.     

SYNTHESIS AND CRYSTAL STRUCTURE OF Ta_3(Te_2)_6

<正> Ta3(Te2)6, Mr = 2074. 04, tetragonal, P4/ncc, a = 9. 204(1) A , c=20,401(8) A, V=1728. 3 A 3, Z = 4, Dc = 7. 97g/cm3, λ(MoKa) = 0. 71073 A . μ= 386, 3cm-1,F(000) = 3372, T= 296K , R= 0. 027, Rw = 0, 029 for 493 observed unique reflections. The structure is composed of infinite [TaTe4] chains along the e axis. In these chains, the Ta sequences distort in such a way that linear Ta, clusters are formed.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRACHLORO-BIS[BIS(2-ETHYLHEXYL)-SULFIDE]-PLATINUM(IV)

<正> C32H68Cl4S2Pt, Pt[(BEHS)2Cl4], Mr=853.9, space group P21/a, a =10.445(3), b=15.012(4), c = 13.506(5) A,β=101.43(3)°,V=2076(1) A3, Z=2, DC=1.37 g·cm-3, MoKa radiation, u= 39.3 cm-1, F(OOO) = 876 e, R = 0.053 for 1790 reflections. Pt(IV) is coordinated by four chloro atoms and two S atoms of BEHS, forming a somewhat distorted octahedron with Pt-S of 2.366 and Pt-Cl of 2.309A. The packing pattern of the long BEHS chain may allow the existence of conformational disorder.     

SYNTHESIS AND CRYSTAL STRUCTURE OF 3-(METHYLMER-CAPTO)PHENANTHRO[9,10-e] 1,2,4-TRIAZINE

<正> The title compound was synthesized by a new method and its crystal structure was determined by X-ray diffraction analysis. C16H11N3S, Mr = 277. 34, triclinic system, space group P1, cell parameters: a = 10. 410(4), b = 17. 953(5), c = 7. 468(3)(?), α=101. 47(3)°,β=110. 85(3)°, γ = 81. 53(3)°, V = 1273.8(8) (?)3, Z = 4 and Dc=1. 45gcm-3. Refinements of full-matrix least-squares converged at R = 0. 053 and Kw = 0.065 for 2794 observed reflections. There are two independent molecules in an asymmetric unit. All non-hydrogen atoms of phenanthro[9,10-e]-1,2,4-triazine make up a 18 18 large conjugated plane.     

SYNTHESIS, SPECTRAL AND MAGNETIC CHARACTERISATION OF SOME BIMETALLIC ALKOXIDES OF NICKEL(Ⅱ)WITH GALLIUM(Ⅲ)AND ZIRCONIUM(IV)

Some interesting bimetallic isopropoxides of nickel(Ⅱ) with gallium(Ⅲ) and zirconium(Ⅳ), Ni[Ga(OPr~1)_4]_2 and Ni[Zr_2(OPr_1)_9]_2 have been synthesized by the interaction of NiCl_2·2Pr~1OH with K[Ga(OPr~1)_4],and K[Zr_2(OPr~1)_9] respectively, in 1:2 molar ratio. These bimetallic isopropoxides undergo facile alcohol interchange reactions with primary alcohols. However, reactions with tertiary alcohols result in the isolation of partially substituted derivatives with the compositions, Ni[Ga(OPr~1)(OBu~t)_3]_2 and Ni[Zr_2(OPr~1)_3(OBu~t)_6]_2. Characterisation of these derivatives has been made on the basis of elemental analyses, infrared, electronic spectral and magnetic susceptibility measurements. These studies suggest an octahedral geometry for nickel(Ⅱ) in the primary bimetallic alkoxides, while in the case of secondary and tertiary derivatives, an equilibrium is suggested between octahedral and tetrahedral forms.##属性不符     

f-ELEMENT/CROWN ETHER COMPLEXES 15. SYNTHESIS AND CRYSTAL STRUCTURE OF ([Lu(OH2)8]Cl3·1.5(12[sbnd]CROWN[sbnd]4)·2H2O

Abstract

The title complex was crystallized at 5°C from a reaction mixture of hydrated LuCl₃ and 12-crown-4 in a solution of CH₃OH:CH₃CN (1:3) after layering in pentane. The crystal and molecular structure of [Lu(OH₂)₈]Cl₃·1.5(12-crown-4)·2H₂O has been determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/c with a=8.816(3), b=23.387(4), c=13.544(2)Å, β=95.14(2)°, and D_calc =1.73 g cm^?3 for Z=4. Least-squares refinement using 3819 independent observed [F₀  5σ(F₀ )] reflections led to the final conventional R value of 0.041. The Lu(III) cation is coordinated to eight water molecules (Lu[sbnd]O average 2.33(3)Å) in an approximate bicapped trigonal prismatic geometry. The crown ether molecules, chloride ions, and uncoordinated water molecules participate in hydrogen bonds to the cation. The hydrogen bonding of the [Lu(OH₂)₈]³⁺ cations to the crown ether molecules results in zigzag chains along c. The chains are further connected by hydrogen bonding to the chloride ions and uncoordinated water molecules. One crown ether resides around a crystallographic centre of inversion and has a C_i , conformation. The second crown has the C₄ conformation normally observed in metal complexes with this ligand.     

CRYSTAL STRUCTUHE OF OXO-BIS[DIETHYLDITHIOCARBAMATO]-MOLYBDENUM(IV)

<正> INTRODUCTION. The existance of an oxido-reduction cycle in the oxo-molybdenum dithiocarbamates, has attracted much attention. In 1974 Ricardreported the crystal and molecular structure of MoO(Pr_2dtc)2, which wereprepared from the reaction of MoO2(Pr_2dtc)2 with pph_3 in tuluene. Herewe report the structure of the title compound, MoO(Et_2dtc)_2 (1) obtainedfrom a reaction Mo(CO)_6 with Et_2NCSSNa in acetonitrile. The structure of1 is very different from the analogue MoO(Pr_2dtc)_2.     

SYNTHESIS,STRUCTURE AND REACTIVITY OF BIS(N-ARYL-IMINOPHOSPHORANYL)METHANES. X-RAY CRYSTAL STRUCTURES OF (4-CH3-C6H4-N˭PPh2)2CH2 AND (4-NO2-C6H4-N˭PPh2)2CH2

Abstract

The synthesis of novel bis(N-aryl-imino-phosphoranyl)methanes of the type CH₂(PR₂?N-Ar)₂ has been accomplished by reaction of methylene-bisphosphines with arylazides. These compounds have been fully characterized by ¹H, ³¹P and ¹³C NMR, IR spectroscopy, Field Desorption Mass Spectroscopy (? FDMS) and elemental analysis. Variable temperature NMR experiments and single crystal X-ray structure determinations of CH₂(PPh₂?N-C₆H₄-CH₃-4)₂ (la) and CH₂(PMe₂?N-C₆H₄-NO₂-4)₂ (1f) reveal that bis(N-aryl-imino-phosphorany1)methane occurs as tautomer 1. Crystals of la are orthorhombic, space group Pcab, with a = 26.602(2), b = 20.521(1), c = 11.8859(7) Å and V = 6488.5(7) ų (2 = 8, R = 0.045 and R_w = 0.066). The crystals of lf are monoclinic, space group C/2c, with a = 20.153(4), b = 5.952(1), c = 16.930(5) Å, β = 106.24(3)° and V = 1949.6(6) ų (Z = 4, molecular symmetry C₂, R_w = 0.051 and R, = 0.079). Both molecules consist of 2 iminophosphoranyl units bridged by a methylene group. The P?N bond distances of 1.568(2) and 1.566(2) Å for la and 1.580(4) Å for lf represent normal values for iminophosphoranyl compounds. The N-C bond lengths of 1.386(2) and 1.390(2) A (la) or 1.372(5) A for If indicate that some electron delocalisation over the N-aryl moiety takes place. In la the electron delocalisation takes place separately in each iminophosphoranyl entity, while in lf electron delocalisation occurs only in the N-aryl-NO₂ moiety.

Compound la is easily deprotonated using lithium-diisopropylamide or NaH and shows typical iminophosphoranyl chemistry, since with CO₂ an aza-Wittig reaction has been found and with HX (X?CI, Br) protonation of both imide nitrogen atoms has been observed.