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1.
Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treatment of 2 with AgNO3 gave the complex [Ag2(TAMMTO)4](NO3)2 · 4MeOH (4) and of 2 and 3 with [Ag(PPh3)2]NO3 gave the complexes [Ag(TAMTTO)(PPh3)2]NO3 · 1.5THF (5) and [Ag(FAMTTO)(PPh3)2]NO3 (6), respectively. All the compounds have been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by 31P NMR spectroscopy. Crystal data for 2 at −80 °C: monoclinic, space group C2/c, a=2319.6(2), b=609.8(1), c=1673.6(2) pm, β=106.14(1)°, Z=8, R1=0.0523; for 4 at −80 °C: triclinic, space group , a=877.6(1), b=1085.2(1), c=1557.7(2) pm, α=77.14(1)°, β=80.87(1)°, γ=78.18(1)°, Z=1, R1=0.0407; for 5 at 20 °C: triclinic, space group , a=1151.1(2), b=1225.1(2), c=1887.4(3) pm, α=78.04(1)°, β=86.20(1)°, γ=76.03(1)°, Z=2, R1=0.0662; for 6 at −80 °C: triclinic, space group , a=1189.7(2), b=1387.8(2), c=1410.9(2) pm, α=94.74(2)°, β=95.12(2)°, γ=112.41(2)°, Z=2, R1=0.0511.  相似文献   

2.
Conductometric investigation on the bis(triphenyl phosphine) ruthenium(II) complex, cis-[RuCl2(L)(PPh3)2] (A) (where PPh3: triphenyl phosphine and L: 2-(2′-pyridyl)quinoxaline, C13N3H9), in dimethylsulfoxide (DMSO) was performed at temperatures ranging from 25 to 50 °C. In addition, cyclic voltammograms of A were recorded on platinum working electrode in dichloromethane (DCM) and dimethylsulfoxide (DMSO) using n-tetrabutylammonium hexafluorophosphate (NBu4PF6) as supporting electrolyte at 25 °C. The molar conductivities (Λ) demonstrate that A behaves as uni-univalent electrolyte in DMSO over the whole temperature range. This behavior can be explained in terms of the replacement upon dissolution of chlorine and PPh3 ligands by DMSO molecules, and consequently, the formation of the ion-pair [RuCl(L)(PPh3)(DMSO)2]Cl [B+Cl] which is dissociated in some extent. The Λ values were analyzed by means of the Lee-Wheaton conductivity equation in order to estimate the limiting molar conductivities (Λo) and the ion-pair association constants (KA) of [B+Cl]. The limiting ion conductivities for the B+ ion were evaluated using n-tetrabutylammonium chloride (NBu4Cl) as “reference electrolyte”. The thermodynamic functions related with the ion association, such as Gibbs free energy , enthalpy , and entropy , were evaluated as well. The mobility of B+ was found to increase linearly with rising temperature and the consequent decrease of the viscosity (η) of DMSO. The KA and values indicate that the association of [B+Cl] increases to some extent with the rise of the temperature followed by the decrease of the dielectric constant (ε) of DMSO. The voltammetric experiments indicated that the couple Ru3+/2+ is reversible and diffusion controlled in DCM and completely irreversible in DMSO.  相似文献   

3.
Two new rhenium(IV) mononuclear compounds of formula NBu4[ReBr4(OCN)(DMF)] (1) and (NBu4)2[ReBr(OCN)2(NCO)3] (2) (NBu4 = tetrabutylammonium cation, OCN = O-bonded cyanate anion, NCO = N-bonded cyanate anion and DMF = N,N-dimethylformamide) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with the space group P21/n, whereas 2 crystallizes in the triclinic one with as space group. In both complexes the rhenium atom is six-coordinated, in 1 by four Br atoms in the equatorial plane, and two trans-oxygen atoms, one of a DMF molecule and another one from a cyanato group, while in 2 by one bromide anion and five cyanate ligands, two of which are O-bonded and three N-bonded, forming a somewhat distorted octahedral surrounding. Magnetic susceptibility measurements on polycrystalline samples of 1 and 2 in the temperature range 1.9-300 K are interpreted in terms of magnetically isolated spin quartets with large values of the zero-field splitting (|2D| is ca. 41.6 and 39.2 cm−1 for 1 and 2, respectively).  相似文献   

4.
Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]3[W4Te4(CN)12] · 9H2O (1) (dien=diethylenetriamine) and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K6[W4Te4(CN)12] · 5H2O/K6[W4Se4(CN)12] · 6H2O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P21 for 1; trigonal, space group for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W4Te4(CN)12}/{W4Se4(CN)12} connected, one another by {Cu(dien)} or {Ni(en)(NH3)} fragments, respectively.  相似文献   

5.
The synthesis of [K]2[CpFe(CN)3] (1) and its pentamethylcyclopentadienyl analog (2) has been described via the photolysis of the corresponding [K][CpFe(CO)(CN)2] salts in methanol in the presence of KCN. The structure of complex 1 has been characterized by means of X-ray crystallography, where the potassium ions are interacting with the N atoms of the cyanide ligands. As expected, the average νCN stretching frequency in the anion is 16 cm−1 higher than that in the more electron-donating pentamethylcyclopentadienyl derivative.  相似文献   

6.
Hydrothermal chemistry was used to prepare the bimetallic organic-inorganic hybrid oxide [Cu(I)Cu(II)2(trz)2Mo4O13(OH)] · 6H2O (1 · 6H2O). The structure consists of chains linked through into a three-dimensional framework. The structures of the simple metal-triazole phases [MoO3(Htrz)0.5] (2) and [Cu(trz)] (3) are also reported. Compound 2 is two-dimensional, constructed from corner-sharing {MoO5N} octahedra. Compound 3 consists of {Cu(trz)}n chains linked through weak Cu?Cu contacts into a virtual layer.  相似文献   

7.
The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4-dmbpy=4,4-dimethyl-2,2-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen atoms of the dmphen molecule (1 and 2) and either one nitrile-nitrogen from a terminal dca ligand (1) or a nitrate-oxygen atom (2) build the equatorial plane whereas the second nitrogen atom of the heterocyclic dmphen fills the axial position (1 and 2). The copper-copper separations through double (1) and single (2) end-to-end dca bridges are 7.1337(7) (1) and 7.6617(7) (2). Compound 3 is a mononuclear copper(II) complex whose structure contains two neutral and crystallographically independent [Cu(4,4-dmbpy)(H2O)(dca)2] molecules which are packed in two different layer arrangements running parallel to the bc-plane and alternating along the a-axis. The copper atoms in both molecules have slightly distorted square pyramidal surroundings with the two nitrogen atoms of the 4,4-dmbpy ligand and two dca nitrile-nitrogen atoms in the basal plane and a water oxygen in the apical position. A semi co-ordinated dca nitrile-nitrogen from a neighbour unit [2.952(6) Å for Cu(2)-N] is in trans position to the apical water molecule in one of the two molecules, this feature representing part of the difference in supramolecular connections in the alternating layers referred to above. Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K reveal the occurrence of weak antiferromagnetic interactions through double [J=−3.3 cm−1 (1), ] and single [J=−0.57 cm−1 (2), ] dca bridges and across intermolecular contacts [θ=−0.07 K (3)].  相似文献   

8.
The ligand exchange reaction of the anionic binuclear rhenium complexes (R = H (1) or Me (2)) has been studied with the carboxylic acids; benzoic acid (3, 4, and 5), fumaric acid (6), and terephthalic acid (7). The exchange with benzoic acid can be controlled by stoichiometry to one, two, or three substitutions. The doubly (4) and triply (5) substituted complexes represent new structural motifs for the triply bridged Re2(CO)6 unit. The dicarboxylic acids fumaric and terephthalic bridge two dirhenium centers. Crystal structure determinations have been carried out for the new complexes synthesized.  相似文献   

9.
One-pot reaction between MnCl2·4H2O, K2tcpd (tcpd2− = [C10N6]2− = (C[C(CN)2]3)2− = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion) and 2,2′-bipyrimidine (bpym = C8H6N4) in aqueous solution yields the new compound [Mn2(bpym)3(tcpd)2(H2O)2] (1). The molecular structure of 1 consists of a centrosymmetrical binuclear complex which includes unprecedented unidentate tcpd ligands with two bidentate and a bis-chelate bpym units. Examination of the intermolecular distances reveals that the dinuclear units are held together by hydrogen bonds involving coordinated water molecules and two nitrile groups of the tcpd ligand, giving rise to a 2D structure overall. Variable-temperature magnetic susceptibility data show the occurrence of slight antiferromagnetic coupling (J = −0.58 cm−1) between the Mn(II) ions through bridging bpym (the exchange Hamiltonian being defined as ).  相似文献   

10.
Hydrothermal reaction of molybdenum oxide and copper(II) source in the presence of 4,4′-bipyridine (4,4′-bpy) afforded three-dimensional covalent framework [CuII(4,4′-bpy)(MoO4)] (1), while reaction with 1,4-diazoniabicyclo[2,2,2]octane (DABCO) in place of 4,4′-bpy and addition of metal molybdenum resulted in one-dimensional chain-like compound . The copper in 1 is divalent and approximately shows trigonal bipyramidal geometry, while in 2 is monovalent and approximately shows T-shaped geometry. The structure of 1 has a three-dimensional pillar-layered framework constructed from bimetallic {CuMoO4} layers bridged by bifunctional ligand 4,4′-bpy. Interestingly, the {CuMoO4} layer in 1 consists of 16-membered {Cu4Mo4O8} rings and 8-membered {Cu2Mo2O4} rings, different from other reported {CuMoO4} layers. The structure of 2 consists a one-dimensional chain that is attached by peripheral {Cu(HDABCO)}2+ units. The chain is constructed from octamolybdates through common corners.  相似文献   

11.
The organometallic Lewis acid, [CpFe(CO)2]+ (Cp = η5-C5H5) reacts with excess dry diethyl ether at low temperatures to form the labile complex [CpFe(CO)2(Et2O)]+[BF4] (1) which is stable at low temperatures and has been fully characterized. Complex 1 in turn reacts with 1-aminoalkanes and α,ω-diaminoalkanes to form new complexes of the type [CpFe(CO)2NH2(CH2)nCH3]BF4 (n = 2-6) (2) and [{CpFe(CO)2}2μ-(NH2(CH2)nNH2)](BF4)2 (n = 2-4) (3), respectively. These complexes have been fully characterized and the mass spectral patterns of complexes 2 are reported. The structures of compounds 2a (n = 2) and 2b (n = 3) have been confirmed by single crystal X-ray crystallography. The single crystal X-ray diffraction data show that complex 2a, [CpFe(CO)2NH2(CH2)2CH3]BF4, crystallizes in a triclinic space group while 2b, [CpFe(CO)2NH2(CH2)3CH3]BF4, crystallizes in an orthorhombic Pca21 space group with two crystallographically independent molecular cations in the asymmetric unit. Furthermore, the reaction of 1 with 1-alkenes gives the η2-alkene complexes in high yield.  相似文献   

12.
The syntheses, crystal structures and properties of compounds [Bu4N]2[Ni(ppdt)2] (1) and [Bu4N]2[Pt(ppdt)2] (2) (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) have been described. Compound 1 crystallizes in P21/c space group (monoclinic system), whereas compound 2 crystallizes in C2/c space group (monoclinic system). The crystal structures of both compounds 1 and 2 have been characterized by C-H?S and C-H?N hydrogen bonding interactions between cation and anions resulting in three-dimensional supramolecular networks in the crystals of 1 and 2, respectively. The acid-base behavior of the ground states of both [Bu4N]2[Ni(ppdt)2] (1) and [Bu4N]2[Pt(ppdt)2] (2) and also the excited state of compound [Bu4N]2[Pt(ppdt)2] (2) in solutions has been studied. The pH dependent changes in the charge transfer absorption and emission spectra are attributed to the protonation on an imine nitrogen of the ppdt ligand. The ground-state basicity constants of the two complexes 1 and 2 have been determined from spectrophotometric analysis by titrating with an weak acid, yielding pKb1 = 8.0 for complex [Bu4N]2[Ni(ppdt)2] (1) and pKb1 = 7.8 for complex [Bu4N]2[Pt(ppdt)2] (2). The excited-state basicity constant pKb1* for complex [Bu4N]2[Pt(ppdt)2] (2) has been determined by a thermodynamic equation using a Förster analysis yielding the value of 1.8. The complex 2 is electrochemically irreversible with an oxidation potential of E1/2 = +0.41 V versus Ag/AgCl in methanol.  相似文献   

13.
Addition of excess CF3CO2H (HTFA) to [Rh2Pt2(CO)7(PPh3)3], I, under nitrogen results in the formation of a salt (X2+ Y2−), which contains only the second example of a di-cationic carbonyl hydride tetra-nuclear cluster, [H2Rh2Pt2(CO)7(PPh3)3]2+, X2+, and a presently partially characterized polymetallic anion Y2−. The di-cation X2+ has been characterized by mass spectrometry and a variety of multinuclear NMR methods. Since there is no difference in the electron count for I and X2+, it is probable that both I and X2+ adopt similar butterfly metallic frameworks with a Rh-Rh hinge; in X2+, there are two bridging hydrides to the same wing-tip Pt but the phosphine site occupancies on the Rh2Pt2-framework in I and X2+ are different.  相似文献   

14.
The reaction of Cd(OAc)2 · 4H2O and 1-alkyl-2-(arylazo)imidazole [RaaiR′ where R = H (a), Me (b); R′ = Me (1/3/5), Et (2/4/6)] and NH4NCS/NaNCO in methanol in 1:2:2 mole ratio has afforded [Cd(RaaiR′)2(NCS)2] (34) and [Cd(RaaiR′)2(NCO)2] (56) complexes. The complexes are characterized by different physicochemical methods and in one case, the structure was confirmed by single crystal X-ray diffraction study for title compounds.  相似文献   

15.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

16.
The organometallic tin(IV) complexes [SnPh2(SRF)2] SRF = SC6F4-4-H (1), SC6F5 (2), were synthesized and their reactivity with [MCl2(PPh3)2] M = Ni, Pd and Pt explored. Thus, transmetallation products were obtained affording polymeric [Ni(SRF)(μ-SRF)]n, monomeric cis-[Pt(PPh3)2(SC6F4-4-H)2] (3) and cis-[Pt(PPh3)2(SC6F5)2] (4) and dimeric species [Pd(PPh3)(SC6F4-4-H)(μ-SC6F4-4-H)]2 (5) and [Pd(PPh3)(SC6F5)(μ-SC6F5)]2 (6) for Ni, Pt and Pd, respectively. The crystal structures of complexes 1, 2, 3, 4 and 6 were determined.  相似文献   

17.
Two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] 1 and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO4 and HPO2(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO4 and HPO3 units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.  相似文献   

18.
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions.  相似文献   

19.
Subsequent addition of 1,2-benzenedithiol (S2-H2) and nBuLi to a solution of [Ru(NO)Cl3 · xMeOH] in THF afforded exclusively the monomeric species NBu4[RuII(NO)(S2)2] (1). Formation of dimeric (NBu4)2[RuII(NO)(S2)2]2 (2) has been confirmed when the deprotonated ligand S2-Li2 was added to [Ru(NO)Cl3 · xMeOH] and allowed to stir for 30 h. The monomer 1 undergoes aerial oxidation to give (NBu4)2[RuIV(S2)3] (3). The reaction between RuCl3 · xH2O and S2-H2 in the presence of NaOMe, afforded the dinulear RuIII species (NMe4)2[RuIII(S2)2]2 (4). A modified method for the preparation of 1 is being employed to synthesize the osmium analogue NBu4[Os(NO)(S2)2] (5) effectively. The solid state structures of 1, 2 and 3 were determined by X-ray crystal structure analysis. A comparison of relevant bond distance data suggests that 1,2-benzenedithiolate acts as an “innocent” ligand.  相似文献   

20.
Bimetallic alkylidene complexes of molybdenum (RF3O)2(ArN)MoCH-SiMe2-CHMo(NAr)(ORF3)2 (1) and (RF3O)2(ArN)MoCH-SiPhVin-CHMo(NAr)(ORF3)2 (2) (Ar = 2,6-C6H3; RF3 = CMe2CF3) have been prepared by the reactions of vinyl silicon reagents Me2Si(CHCH2)2 and PhSi(CHCH2)3 with known alkylidene compound PhMe2C-CHMo(NAr)(ORF3)2. Complexes 1 and 2 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1 and 2 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and predominant cis-units content in the case of 2.  相似文献   

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