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1.
Some cobalt(II) complexes of 4,6-dimethylpyrimidine-2(1H)-one (HL) have been prepared and studied by infrared and electronic spectra and by magneto-chemical and conductometric measurements. The ligand is coordinated through the unprotonated ring-nitrogen atom and in one case also through the carbonylic oxygen atom. The “blue” complexes [CoX2 · 2HL] (X2 = Cl2, ClBr, Br2, (NCS)2) and [CoX2 · 2HL] · 2HL (X = Cl, Br) have a distorted C2v [CoX2N2] coordination; the thiocyanate ion is N-bonded to the metal. The “green” complexes CoX2 · 2HL (X = Cl(4H2O), Br) have a square-pyramidal [CoX2N2O] coordination. The “pink” CoX2 · 4HL · nH2O (X = ClO4, n = 2; X = BF4, n = 8; X = F3Ac, n = 4) and “cream” CoX2 · 4HL · 6 H2O (X = I, ClO4) complexes have an octahedral coordination; only the F3Ac? ion is coordinated. The “cyclamen” CoAcL · 2HL · 2 H2O and Co3Ac4L2 · 2HL · 2H2O complexes have a polynuclear constitution; the Ac? ion behaves as bidentate ligand.  相似文献   

2.
New complexes having the formulae [L2CoX2] and [LCuCl2], [LCuCl] and [LCu](ClO4)2 where L?=?(2-thiophene)-(5,6-diphenyl-[1,2,4]-triazin-3-yl)hydrazone TDPTH; X?=?Cl, OAc or ClO4 have been synthesized and characterized on the basis of elemental analyses, conductance, magnetic moments and infrared, electronic and ESR spectral data. The IR spectra indicate that TDPTH is a neutral bidentate ligand, coordinating via a triazine-N and azomethine-N in [L2CoX2] and [LCuCl2] with the thiophene-S not coordinated but is tridentate in [LCuCl] and [LCu](ClO4)2 through the same two nitrogen atoms and thiophene-S. The magnetic moment and electronic spectral data suggest a distorted octahedral structure for Co(II) complexes, a dimeric square pyramidal geometry for [LCuCl2] through chloride bridges and a dimeric diamagnetic, four-coordinate copper in [LCu](ClO4)2 through thiophene-S bridges. The X-band ESR spectra of Co(II) complexes, in the solid state, are rhombic with three g values consistent with a high-spin distorted octahedral structure. The X-band ESR spectrum of the powdered sample of both [LCuCl2]·2H2O and [LCu](ClO4)2 at room temperature and at 77?K showed only one broad signal due to?ΔM s?=?±?1 transition and a weak signal due to the forbidden?ΔM s?=?±?2 transition, indicating an antiferromagnetic interaction between copper(II) centers whereas [LCuCl] is ESR silent, indicating a monovalent copper ion in this complex.  相似文献   

3.
The optical yield in enantioselective hydrogenation of methyl -acetamidocinnamate over mono- and diphosphine cobalt(II) complexes CoX2L2 [where X = Cl or CF3SO3, L = (+)-(1S,2S,5R)-neomenthyl-diphenylphosphine or L2' = (-)-(R,R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane], which are generated in situ, in the presence of sodium tetrahydridoborate increases with rise in the phosphine-to-metal ratio and hydrogen pressure. The maximal optical yields of (+)-(S)-N-acetylphenylalanine methyl ester attain 40% (CoX2L2) and 42% (CoX2L2').  相似文献   

4.
Pseudochalcogeno Compounds. XI. On a New Type of Pseudochalcogeno-Modified Phosphates The preparation of pseudochalcogenophosphates of the general formulas [PO3Y]3? and [P2O7-nYn]4? (Y = C(CN)2, n = 1, 2) is described. Chromatography of sodium salts, the formation of silver and calcium salts, characteristic IR and 31P-NMR data are discussed.  相似文献   

5.
Summary Cobalt(II) complexes of 4-amino-2,6-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine (taz) were prepared by reacting the triazine with the corresponding cobalt salt. The isolated compounds were of the types: [CoCl2(taz)], [CoX2(taz)2(H2O)2] (X = Br or I), [CoX2(taz)2] (X = Br, SCN or NO3) and [Co(taz)2(H2O)2]X2(X = C1O4, BF4 or NO3). Conductance, magnetic and spectroscopic (i.r. and vis.) data were used for structural assignments. Pseudooctahedral and pseudotetrahedral structures are proposed for the complexes, with the triazine molecule acting either as a monodentate nitrogen-donor or a bidentate nitrogen-sulphur-donor ligand.  相似文献   

6.
Pseudoelement Compounds. II. Quantum Chemical Studies on Pseudoelement Modified Nitrite Ions [EO2?nYn]? (E = N, C(CN); Y = C(CN)2) The electronic structure and the ambidence of pseudochalcogen modified nitrite ions are discussed on the basis of a quantum chemical MNDO study in connection with structural, ESCA and 13C NMR data.  相似文献   

7.
《Polyhedron》1987,6(5):921-929
Complexes of the terdentate ligands bis[2-diphenylphosphino)ethyl]benzylamine (DPBA) and bis[2-(diphenylarsino)ethyl]benzylamine (DABA) with Co(II), Ni(II), Pd(II), Pt(II), Rh(III), Ir(III), Rh(I) and Ir(I) are reported. The ligand DPBA reacts with Co(II) ion to form two types of complexes: a high-spin, paramagnetic, tetrahedral Co(II) complex of composition [CoCl(DPBA)]Cl and a low-spin, paramagnetic, square-planar complex of composition [CoBr(DPBA)]B(C6H5)4. The reaction of DPBA with Ni(II) ion in methanol yields low-spin, diamagnetic, square-planar complexes of type [NiX(DPBA)]Y [X = Cl, Br or I; Y = Cl or B(C6H5)4]. Four-coordinate, square-planar, cationic complexes of type [MY(L+[M = Pd(II), Pt(II), Rh(I) or Ir(I); Y = Cl or P(C6H5)3; L = DPBA or DABA], were obtained on reaction of L with various starting materials containing these metal ions. Reaction of DPBA and DABA with rhodium and iridium trichlorides gave octahedral, neutral complexes of general formula [MCl3(L)] (M = Rh or Ir, L = DPBA or DABA). All the complexes were characterized on the basis of their elemental analysis, molarconductance data, magnetic susceptibilities, electronic spectra, IR spectral measurements, and1H and31P-{1H} NMR spectral data.  相似文献   

8.
Synthesis and Structure of Crown Ether Complexes of Potassium Hexachlorodipalladate(II) and -diplatinate(II) K2[MCl4] (M ? Pd, Pt) reacts with an excess of crown ether 18-crown-6 in water to give the crown ether complexes of potassium hexachlorodipalladate(II) and -diplatinate(II) [K(18-cr-6)]2[M2Cl6] (M ? Pd, 1 ; M ? Pt, 3 ), respectively, and in methylene chloride to give those of potassium tetrachloropalladate(II) and -platinate(II) [K(18-cr-6)]2[MCl4] ( 1 ) (M ? Pd, 2 ; M ? Pt, 4 ), respectively. 1 - 4 are characterized by microanalysis, NMR (1H, 13C), and vibrational spectroscopy. The X-ray structure analyses of the isotypic complexes 1 (P21/c; a = 10,9678(8), b = 8,2991(7), c = 22,469(2) Å, β = 98,523(5)°; Z = 2) and 3 (P21/c; a = 10,934(3), b = 8.376(3), c = 22,410(5) Å, β = 98,77(3)°; Z = 2) reveal [M2Cl6]2? anions of nearly D2h symmetry and [K(18-cr-6)]+ cations, in which the distance of K+ to the mean plane of the crown ether defined by its six oxygen atoms amounts to 0,830(4) Å in 1 and 0,821(2) Å in 3 , respectively. There are tight contacts between cations and anions (d(K-Cl): 3,341(2)/3,260(2) Å ( 1 ); 3,348(4)/3,259(4) Å ( 3 )).  相似文献   

9.
This work describes the synthesis, characterisation and reactivity of new methylallyl Pd(II) complexes that contain bidentate 2-(methylthio-N-benzylidene)anilines as ligands. The reaction of the binuclear complex [(η3-Me-allyl)Pd(μ-Cl)2] with AgBF4 causes the total abstraction of the chloride bridges, with the subsequent formation of an intermediary fragment of Pd(II). This fragment in turn reacts with neutral bidentate 2-(methylthio-N-benzylidene)anilines to give cationic complexes of Pd(II) of general formula [(η3-Me-allyl)Pd(η2-S,N-MeSC6H4NCHC6H4(X)Y)]BF4 [X=H, Y=H (1); X=F, Y=H (2); X=Me, Y=H (3); X=H, Y=Cl (4); X=H, Y=Me2N (5); X=H, Y=NO2 (6)]. The new complexes were characterised by means of elemental analysis, IR, NMR [1H, 19F{1H}, 13C{1H}, 31P{1H}, Dept, 1H-1H-COSY, HSQC, HMBC] and mass spectroscopies. The reaction of the Pd(II) complexes with nucleophiles such as NaI, (EtO)2PS2K, KCN, KSCN or NaH lead to the deco-ordination of the bidentate ligands to give dimeric or polymeric complexes of Pd(II). The reactivity pattern observed is discussed by a theoretical analysis based on Fukui functions.  相似文献   

10.
Osmium(II) Phthalocyanines: Preparation and Properties of Di(acido)phthalocyaninatoosmates(II) “H[Os(X)2Pc2?]” (X = Br, Cl) reacts in basic medium or in the melt with (nBu4N)X forming less stable, diamagnetic, darkgreen (nBu4N)2[Os(X)2Pc2?]. Similar dicyano and diimidazolido(Im) complexes are formed by the reaction of “H[Os(Cl)2Pc2?]” with excess ligand in the presence of [BH4]?. The cyclic voltammograms show up to three quasireversible redoxprocesses: E1/2(I) = 0.13 V (X = CN), ?0.03 V (Im), ?0.13 V (Br) resp. ?0.18 V (Cl) is metal directed (OsII/III), E1/2(II) = 0.69 V (Cl), 0.71 V (Br), 0.83 V (CN), 1.02 V (Im) is ligand directed (Pc2?/?) and E1/2(III) = 1.17 V (Cl) resp. 1.23 V (Br) is again metal directed (OsIII/IV). Between the typical “B” (~16.2 kK) and “Q” (~29.4 kK), “N regions” (~34.1 kK) up to seven strong “extra bands” of the phthalocyanine dianion (Pc2?) are observed in the uv-vis spectrum. Within the row CN > Im > Br > Cl, most of the bands are shifted slightly, the “extra bands” considerably more to lower energy in correlation with E1/2(I). The vibrational spectra are typical for the Pc2? ligand with D4h symmetry. M.i.r. bands at 514, 909, 1 173 and 1 331 cm?1 are specific for hexa-coordinated low spin OsII phthalocyanines. In the resonance Raman (r.r.) spectra polarized, depolarized or anomalously polarized deformation and stretching vibrations of the Pc2? ligand will be selectively enhanced, if the excitation frequency coincides with “extra bands”. With excitation at ~19.5 kK the intensity of the symmetrical Os? X stretching vibration at 295 cm?1 (X = Cl), 252 cm?1 (X = Im) and 181 cm?1 (X = Br) is r.r. enhanced, too. The asymmetrical Os? X stretching vibration is observed in the f.i.r. spectrum at 345 cm?1 (X = CN), 274 cm?1 (X = Cl), 261 cm?1 (X = Im) and 200 cm?1 (X = Br).  相似文献   

11.
Mn[N(SiMe3)2]2(THF) ( I ) (Me = methyl, THF = tetrahydrofuran) was obtained on large scale from “active” MnCl2 and LiN(SiMe3)2 in THE in 85–93% yield. The novel, theoretically interesting tetra-coordinated Mn[N(SiMe3)2]2L2 series was derived from I , where L = THF, pyridine and t-butyleyanide. All these species are quite stable thermally and exhibit exteme oxygen sensitivity. Preparation, properties, and reactions of unsymmetrically substituted (“hemi”) X? Mn? Y type compounds are presented also, where X = ? Cl, ? NO3 and n = butyl, and Y = ? N(SiMe3)2 and ? OR. From Cl? Mn? N(SiMe3)2, with or without coordinated THF being present, the unusual (Mn{SiMe3)2, was isolated as yellow crystals. The “hemi” Mn(II)-system exhibits only moderate thermal stability and tends to disproportionate. Many derivatives are photosensitive, especially with UV light.  相似文献   

12.
Ruthenium(II)-Phthalocyaninates(1–): Synthesis and Properties of (Halo)(carbonyl)phthalocyaninato(1–)ruthenium(II) Brown-violet (halo)(carbonyl)phthalocyaninato(1–)ruthenium(II), [Ru(X)(CO)Pc?] (X = Cl, Br) is prepared by oxidation of [Ru(X)(CO)Pc2?]? with the corresponding halogen or dibenzoylperoxide. The eff. magnetic moment μeff = 1.74 (X = Cl), 1.68 μB (Br) confirms the presence of a low-spin RuII complex of the Pc? radical. Accordingly, only the first ring oxidation at ~0.64 V and the first ring reduction at ~ ?1.19 V is observed in the cyclovoltammogram of [Ru(X)(CO)Pc2?]?. The UV-VIS-NIR spectra characterizing a monomeric Pc? radical with intense π-π* transitions at 14500, 19800, 25100 and 33900 cm?1 are compared with those of [Ru(Cl)2Pc?] and of monomeric as well as dimeric [Zn(Cl)Pc?]. The IR and resonance Raman(RR) spectra are characteristic for a Pc? radical, too. Diagnostic in-plane vibrations of the Pc? ligand are in the IR spectrum at 1071, 1359, 1445 cm?1 and in the RR spectrum (λ0 = 488.0 nm) at 567, 1597 cm?1. v(C? O) at 1950 cm?1 and v(Ru? X) at 260 (X = Cl) resp. 184 cm?1 (X = Br) are observed only in the IR spectrum.  相似文献   

13.
Pseudoelement Compounds. IV. Modification of the Ions Sulfite [SO2Y]2?, Sulfate [SO4?nYn]2?, and Sulfonate [RSO2Y]? by Introducing Pseudochalcogen Groups NCN and C(CN)2 . Described is the synthesis of pseudochalcogen modified sulfites M2[SOY2], sulfates M2[SO4?nYn] (Y = NCN), and arylsulfonates M[RSO2Y] (Y = NCN, C(CN)2). The 13C-NMR and IR spectra of the new compounds are discussed.  相似文献   

14.
Two complex salts, i.e., 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates, [H2(Crypt-222)][MnCl4] · 1.5H2O (I) and [H2(Crypt-222)][ZnCl4] · 2H2O (II) were synthesized and their crystal structures were studied by X-ray diffraction. Crystals I and II are trigonal (space group R \(\bar 3\) c, Z = 12); I: a = 11.033, c = 77.775 Å; II: a = 11.046, c = 77.555 Å (the structures were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.056 (I) and 0.065 (II) for all 2634 (I) and 2636 (II) independent reflections; CAD-4 automated diffractometer, λMoK α). The [MnCl4]2? or [ZnCl4]2? anion in structures I or II and the 2.2.2-cryptand dication (with two protonated N atoms) lie on crystal axis 3. The dication contains trifurcate hydrogen bonds N+-H(…O)3. The bond lengths and bond angles in tetrahedral anions [MnCl4]2? or [ZnCl4]2? are disproportional, probably, due to the Jahn-Teller effect. The molecules of water of crystallization in crystals I, II are disordered over two positions.  相似文献   

15.
Ag/CuI Mixed Occupancy in the Crystal Structures of the Copper(II) Cyanoargentates Cu(NH3)(py)Ag3?xCux(CN)5 · py From pyridine and ammonia containing CuII solutions, to which K[Ag(CN)2] and in part KCu(CN)2/KCN has been added, we obtained single crystals of mixed-valent copper compounds of variable composition Cu(NH3)-(py)Ag3-xCux(CN)5 · py. The phases corresponding to x = 0.39(1) ( I ) and to x = 1.243(6) ( II ) were characterized by X-ray structure analysis. They are isomorphous and crystallize with Z = 4 in the monoclinic space group P21/c. The lattice constants for I [and II , resp.] are: a = 923.8(2) [901.4(2)], b = 1226.8(2) [1227.3(2)], c = 1809.8(4) [1783.5(2)] pm, β = 91.41(3) [91.02(1)]°. The CuII cation shows trigonal bipyramidal [CuN5] coordination, with the neutral ligands in axial positions (mean value Cu? N for II : 201 pm), three N atoms of cyano bridges in equatorial ones (Cu? N: 206 pm). One of these bridges stems from a trigonal unit [AgCN(NC)2], the central atom of which is substituted by CuI to an extent of 39% in I , and completely in II . The two other bridges originate from two [Ag(CN)2]? groups, of which the more bent one may be partially occupied by CuI as well (24% in II ). The units mentioned are connected into meshes of elongated hexagons and further into puckered layers within the (010) plane, interpenetrating each other in pairs. A threedimensional linking of layers occurs by the trigonal Ag/CuI species forming centrosymmetric dimers, in which the metal coordination is completed to tetrahedral by a C-atom of the corresponding neighbouring group and short metal-metal distances of 279.1(3) pm in I and 264.1(1) pm in II appear. Details and relations are discussed.  相似文献   

16.
Cationic palladium(II) and platinum(II) complexes with chelate ylides and neutral ligands of the type, [MCl (Y) (L)]+BPh4? (M  Pd or Pt; Y  bdep or bdmp*; L = 4-methylpyridine, 3,5-dimethylpyrazole, PPh3, PCy3, PMePh2, P(OMe)3, AsPh3 or SbPh3) and [M(bdep) (4-methylpyridine)2] (BPh4)2 (M = Pd or Pt) were prepared and characterized by means of infrared and 1H NMR spectra.  相似文献   

17.
Novel neutral biimidazolate or bibenzimidazolate palladium(II) and platinum(II) complexes of the type M(NN)2(dpe) [M = Pd, Pt; (NN)22? = BiIm2?, BiBzIm2?. dpe = 1,2-bis(diphenylphosphino) ethane] have been obtained by reacting MCl2(dpe) with TI2(NN)2. Complexes M(NN)2(dpe) which are Lewis bases react with HClO4 or [M(dpe)(Me2CO)2](ClO4)2 to yield, respectively, mononuclear cationic complexes of general formula [M{H2(NN)2](dpe) (M = Pd, Pt; H2(NN)2 = H2BiIm, H2BiBzIm) and homobinuclear palladium(II) or platinum(II) cationic complexes of the type [M2{μ - (NN)2}(dpe)2](ClO4)2. Reactions of M(BiBzIm)(dpe) with [Rh(COD) (Me2CO)X](ClO4) render similar heterobinuclear palladium(II)-rhodium(I) and platinum(II)-rhodium(I) cationic complexes, of general formula [(dpe)M(μ-BiBzIm)Rh(COD)](ClO4) (M = Pd, Pt; COD = 1,5-cyclooctadiene). Di- and mono-carbonyl derivatives [(dpe)M(μ-BiBzIm)Rh(CO)L](ClO4) (M = Pd, Pt; L = CO, PPh3) have also been prepared. The structures of the resulting complexes have been elucidated by conductance studies and IR spectroscopy.  相似文献   

18.
Mercury(II)-Induced Hydrolysis of Mixed Hexahalo-Osmates(IV) The strong hydrolytic activity of Hg2+ ions on complexes [OsXnI6?n]2?, X = Cl or Br; n = 1 – 5, is due to electrophilic attack at the I ligands. Small amounts of Hg2+ remove only one I. The very stable [HgI]+ and [HgI2] are formed along with the corresponding pentahalo-monaquo-osmates(IV). In cis-[OsCl4I2]2? and fac-[OsCl3I3]2? ligands rearrange during hydrolysis giving the thermodynamically favoured I? Os? H2O axis. Other mono- and bivalent cations have only a slight catalytic effect on the aquation, increasing with the size from Mg2+ to Ba2+.  相似文献   

19.
Studies on Polyhalides. III. Crystal Structures of [Cu(NH3)4I2 · I2] and [Cu(NH3)4I3]I3 Tetramminecopper(II)tetraiodide [Cu(NH3)4I2 · I2] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH3)4I3]I3 (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I42? (I) or I3? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I42? (I) or I3? (II). Therefore infinite planar zigzag chains of units [Cu(NH3)4I4] (I) or [Cu(NH3)4I3]+(II) are resulting. The counterion I3? (II) is intercalated between these chains.  相似文献   

20.
Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6], and [Ph4P]2[Se(Se5)2] By symproportionation of elemental selenium and SeCl4 in polar protic solvents the novel chloroselenates(+II), [SeCl4]2? and [Se2Cl6]2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph3(C2H4OH)P]2[SeCl4] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl4]2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph4P]2[Se2Cl6] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se2Cl6]2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se5)2]2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph4P]2[Se(Se5)2] (space group P21/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se5)2]2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se5]2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.  相似文献   

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