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1.
《Inorganica chimica acta》1988,148(1):31-36
The reactions of R2SnX2 (R = Ph, Me; X = Cl, Br) with excess halide, tributylphosphine, tricyclohexylphosphine and tributylphosphine oxide have been investigated in dichloromethane solution by tin-119 and phosphorus-31 NMR techniques. R2SnX2 form five coordinate 1:1 adducts with halide and phosphine (phos) ligands whilst both 1:1 and 1:2 adducts are formed with tributylphosphine oxide (L). Tin-119 spectra imply that Ph2SnX2(phos) has the phosphine in the equatorial position of a trigonal bipyramid. At low temperature there is evidence for a slow intramolecular twist mechanism between octahedral isomers of Ph2SnCl2L2. The stereochemistry of the complexes Ph2SnX2L2 differ between chloro and bromo compounds and no mixed halide complex is observed. In the case of the bromo system only, the 1:3 adduct [Ph2SnBrL3]+Br− is formed. Ph3SnCl does not react with phosphines but it does give 1:1 adducts with Cl−, L and pyridine. All the adducts have similar tin-119 chemical shifts which is consistent with the phenyl groups being equatorial in the five coordinate trigonal bipyramidal adducts. Ph4Sn does not form adducts with X−, L or phosphine. 相似文献
2.
《Inorganica chimica acta》1988,147(2):143-150
The crystal structures of trans- and cis-bis(diphenylphosphino) ethene (1, 2) have been determined by single crystal X-ray diffraction. The conformation of these free ligands is compared with structural data available in the literature for the corresponding 1:2 complexes with gold(I) chloride (4, 5). In the cis-ligand 2 the conformation of the Ph2P-groups is such, that the molecule approaches non-crystallographic Cs symmetry with the lone pairs at phosphorus pointing towards each other. Upon addition of AuCl, rotation of one Ph2P group around the PC bond by approximately 60° leads to a structure for 5 which allows an intramolecular Au···Au contact of 3.05(1)Å. The trans-ligand 1 undergoes little structural change upon adduct formation, but intermolecular Au···Au contacts of 3.043(1) Å are secured through aggregation. The synthesis, properties and 197Au Mössbauer spectra of 1:1 and 1:2 complexes of 1 and 2 with AuCl are summarized with reference to a recent controversy in the literature.The crystal structure of bis(diphenylphosphino)- methane (3) has also been determined and the results compared with those published previously for the 1:2 complex with AuCl (7, crystallographic C2 symmetry, Au···Au distance 3.351(2) Å). There is very little change of the ligand conformation upon coordination. 相似文献
3.
Girasolo MA Canfora L Sabatino P Schillaci D Foresti E Rubino S Ruisi G Stocco G 《Journal of inorganic biochemistry》2012,106(1):156-163
New organotin(IV) complexes of 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) and 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine (dptp) with 1:1 and/or 1:2 stoichiometry were synthesized and investigated by X-ray diffraction, FT-IR and 119Sn Mössbauer in the solid state and by 1H and 13C NMR spectroscopy, in solution. Moreover, the crystal and molecular structures of Et2SnCl2(dbtp)2 and Ph2SnCl2(EtOH)2(dptp)2 are reported. The complexes contain hexacoordinated tin atoms: in Et2SnCl2(dbtp)2 two 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine molecules coordinate classically the tin atom through N(3) atom and the coordination around the tin atom shows a skew trapezoidal structure with axial ethyl groups. In Ph2SnCl2(EtOH)2(dptp)2 two ethanol molecules coordinate tin through the oxygen atom and the 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine molecules are not directly bound to the metal center but strictly H-bonded, through N(3), to the OH group of the ethanol moieties; Ph2SnCl2(EtOH)2(dptp)2 has an all-trans structure and the C-Sn-C fragment is linear. On the basis of Mössbauer data, the 1:2 diorganotin(IV) complexes are advanced to have the same structure of Et2SnCl2(dbtp)2, while Me2SnCl2(dptp)2 to have a regular all-trans octahedral structure. A distorted cis-R2 trigonal bipyramidal structure is assigned to 1:1 diorganotin(IV) complexes. The in vitro antibacterial activities of the synthesized complexes have been tested against a group of reference pathogen micro-organisms and some of them resulted active with MIC values of 5 μg/mL, most of all against staphylococcal strains, which shows their inhibitory effect. 相似文献
4.
《Inorganica chimica acta》1987,132(2):217-222
XPd(μ-dppm)2Pt(C6F5) (X = Cl (I), Br (II)) have been prepared by reacting Pd2(dba)3·CHCl3 and PtX- (C6F5)(η1-dppm)2. Reaction of complex I with SnCl2 gives the SnCl3− derivative, whilst ligands L (PPh3, P(OPh)3, SbPh3) render the cationic complexes. The species R2N+, SO2 or MeOOC)CCCOOMe insert into the PdPt bond of I to give A-frame Pd(II)- Pt(II) complexes. The reactions of CIPd(μ-dppm)2- Pt(C6F5) with isonitriles CNR (R = p-Tol, Cy) lead to products containing either terminal or inserted isocyanide or both. 相似文献
5.
The synthesis of the solid adducts Me3SnOH · Me3 SnNCO, Me3SnOH · Me3SnNCS, Me3SnOH · Me3PbN3, Ph3SnOH · Ph3SnN3 is reported. The compounds have been investigated by infrared and Mössbauer spectroscopy. Their structure probably consists of polymeric OH-R3Sn-X-R3Sn(Pb) chains in which hydroxyl and pseudohalide (X) groups are bridging pentacoordinate tin atoms. In contrast to the triphenyl compound, the trimethyl derivatives show evidence of hydrogen bonding between adjacent chains. 相似文献
6.
Augusto CingolaniEffendy Fabio Marchetti Claudio PettinariRiccardo Pettinari Brian W SkeltonAllan H White 《Inorganica chimica acta》2002,329(1):100-112
Silver(I) acylpyrazolonate derivatives of formula [Ag(Q)(R3P)]2 and [Ag(Q)(R3P)2], (QH=1-phenyl-3-methyl-4-R′(CO)-pyrazol-5-one; QOH, R′=furane; QSH, R′=thiophene; R=Ph, Cy, o-tol), have been synthesised and characterised, both in the solid state and in solution. The derivatives [Ag(Q)(R3P)]2 contain dinuclear AgO2NP units with the acylpyrazolonate coordinating in a bridging O,O′-Q-N fashion. The [Ag(Q)(R3P)2] are tetrahedral species, with the distortion from ideal geometry increasing with the bulk of the phosphine. The [Ag(Q)(R3P)2] derivatives are fluxional in chloroform solution when R3P is sterically hindered (R=Cy or o-tol), dissociating partially to the [Ag(Q)(R3P)] fragment and free R3P. [Ag(QS)(Ph3P)]2 reacts with 1-methyl-2-mercaptoimidazole (Hmimt) affording the compound [Ag(Hmimt)(Ph3P)(QS)] and [Ag(QO)(Ph3P)]2 reacts with 1-methyl-imidazole (Meim) affording the compound [Ag(Meim)(Ph3P)(QO)], whereas [Ag(QS)(Ph3P)]2 reacts with 1,10-phenanthroline (phen), affording the compound [Ag(phen)(Ph3P)](QS). Finally [Ag(QS)(Ph3P)2] reacts with phen producing the ionic species [Ag(phen)(Ph3P)2](QS). 相似文献
7.
The crystal structure of the compound [(Ph2PCH2CH2PPh2)Pt(3,5-Me2pzH)2][BF4]2·CH2Cl2 has shown that the ligands around the Pt atom are approximately in a square planar coordination, whereas the pyrazole rings point roughly in the same direction, away from the coordination plane. This unusual conformation is probably due to the hydrogen bonds with fluorine atoms of the BF4? anion. Bond distances and angles are compared with those in other pyrazole complexes. 相似文献
8.
《Journal of enzyme inhibition and medicinal chemistry》2013,28(4):557-564
Four complexes [Pd(L)(bipy)Cl]·4H2O (1), [Pd(L)(phen)Cl]·4H2O (2), [Pt(L)(bipy)Cl]·4H2O (3), and [Pt(L)(phen)Cl]·4H2O (4), where L = quinolinic acid, bipy = 2,2’-bipyridyl, and phen = 1,10-phenanthroline, have been synthesized and characterized using IR, 1H NMR, elemental analysis, and single-crystal X-ray diffractometry. The binding of the complexes to FS-DNA was investigated by electronic absorption titration and fluorescence spectroscopy. The results indicate that the complexes bind to FS-DNA in an intercalative mode and the intrinsic binding constants K of the title complexes with FS-DNA are about 3.5?×?104 M?1, 3.9?×?104 M?1, 6.1?×?104 M?1, and 1.4?×?105 M?1, respectively. Also, the four complexes bind to DNA with different binding affinities, in descending order: complex 4, complex 3, complex 2, complex 1. Gel electrophoresis assay demonstrated the ability of the Pt(II) complexes to cleave pBR322 plasmid DNA. 相似文献
9.
Abdul Ghany M. Al-Daher Kenneth W. Bagnall Carla Bisi Castellani Franco Benetollo Gabriella Bombieri 《Inorganica chimica acta》1984,95(5):269-277
The complexes M(NCS)4·xL (x = 2, M = U, L = Me3CCON(Pri)2(dippva); x = 3, M = Th, L = Me2CHCON(Pri)2(dipiba) and dippva, M = U, L = EtCON(Pr1)2(dippa), dipiba and dippva; x = 4, M = Th, L = MeCON(Pri)2(dipa), dippa and dipiba, M = U, L = dipa, dippa) and the solvates M(NCS)4·4dipa·CH2Cl2 (M = Th, U) have been prepared. Their i.r. and u.v.-visible (M = U only) spectra are reported. The crystal and molecular structure of U(NCS)4(dipa)4· CH2Cl2 has been determined by the heavy-atom method from X-ray diffractometer data and refined by least squares to R 0.029 for 1135 independent reflections. The crystal is tetragonal, space group P21c, with Z = 2, a = 15.663(4) and c = 10.512(3) Å. The coordination geometry about the 8-coordinate uranium atom is dodecahedral with the N atoms of the NCS groups occupying the dodecahedral A sites and the ‘dipa’ O atoms the B sites. The bonding distances of UO and UN are 2.363(8), and 2.444(11) Å respectively. 相似文献
10.
The polymeric structure of the complex, [SnCl4(H2O)2]18-crown-6·2H2O, prepared by the addition of a solution of SnCl4 to 18-crown-6, has been determined by X-ray analysis. The structure has been solved by three-dimensional Patterson-Fourier synthesis to a conventional R-factor of 0.13, by using 1394 reflections with I>3σ(I). The crystals are monoclinic, with a = 15.753(3), b = 15.072(3), c = 12.209(4), β = 97.77°(1.0), z = 4, and space group P21/a. The tin atom is octahedrally coordinated to four chlorine atoms and two water molecules in cis positions. A very complex network of hydrogen bonding links together the tin coordination octahedron, the two water hydration molecules, and the two crystallographically-different half crown-ethers. 相似文献
11.
Rh(I), Ir(I), Pd(II) and Pt(II) metal complexes of bis(2-diphenylphosphino)ethyl)benzylamine(DPBA) and bis(2-diphenylarsino)ethyl)benzylamine (DABA) have been synthesized using various starting materials. Reaction of RhCl(CO)(AsPh3)2 with DPBA or DABA in methanol resulted in the formation of cationic complexes of the composition, [Rh(CO)(L)]Cl (L = DPBA or DABA). Interaction of [IrCl(COD)]2 with DPBA in benzene resulted in the formation of a neutral complex [IrCl(DPBA)]. Reaction of [PdCl2(COD)] with the ligand DPBA in benzene resulted in a cationic complex of the composition [PdCl(DPBA)]Cl. Interaction of [PdCl(DPBA)]BPh4 with SnCl2 gave the complex [Pd(SnCl3)(DPBA)]BPh4. The ligands DPBA and DABA react with PtCl2(COD) in acetone to give neutral, Pt(II) complexes of the type, [PtCl2L] (L = DPBA or DABA). All the complexes were fully characterized by elemental analysis, conductivity measurements, IR and far-IR and 31P{1H} NMR spectral data. 相似文献
12.
Two competing reactions are present when benzene solutions of the five co-ordinate complex CrCl3·2NMe3 are treated with donor molecules viz., a) ligand substitution via solvolysis of metal-nitrogen bonds and b) the independent decomposition of the bis-trimethylamine adduct into tri-μ-chloro-trichlorotris(trimethylamine) dichromium(III), Cr2Cl6(NMe3)3, and trimethylamine. For all but very feeble donors reaction a) predominates and in the ensuing adduct formation the chromium(III) ions assume hexacoordination, e.g. pyridine and tetrahydrofuran react immediately to give the corresponding CrCl3·3L complexes. Reaction b) shows second order kinetics with a rate constant k = 0.160 1 mole−1 sec−1 The spectral and magnetic properties of the binuclear compound Cr2Cl6(NMe3)3 have been interpreted in terms of adjacent six co-ordinate metal atoms and a proposed structure is based on two fused octahedra sharing a common trigonal face. The product obtained on treatment of CrCl3·2NMe3 with AgClO4 involves only bidentate (C2v) perchlorate ions as co-ordinated ligand and is formulated as Cr(ClO4)3. 相似文献
13.
Michael Müller Thomas Weyhermüller Eckhard Bill K. Wieghardt 《Journal of biological inorganic chemistry》1998,3(1):96-106
The asymmetrically coordinated complex [{L(Ph2acac)FeIII}(μ-O){FeIII(Cl4-cat)L}](BPh4)·1.5toluene has been synthesized and structurally characterized (Ph2acac–=1,3-diphenylpropane-1,3-dionate, Cl4-cat2–=tetrachlorocatecholate, L=1,4,7-trimethyl-1,4,7-triazacyclononane). This species can be electrochemically oxidized and reduced by one electron, respectively, yielding two species which both have an S=1/2 ground state. It is shown that the oxidation is ligand-centered, affording a coordinated semiquinonate(1–) ligand with S=1/2 which is antiferromagnetically coupled to a high-spin FeIII ion (S=5/2) yielding an S=2 state which, in turn, is antiferromagnetically coupled (through the oxo bridge) to the second high-spin FeIII ion (S=5/2) yielding the observed S=1/2 ground state. In contrast, the reduction is metal-centered generating a mixed-valent species with an [FeIII-O-FeII]3+ core; intramolecular antiferromagnetic coupling again produces an S=1/2 ground state. The symmetrical complex [{LFeIII(Ph2acac)}2(μ-O)](ClO4)2 has also been synthesized, as have the mononuclear species [LFeII(Ph2acac)Cl] and [LFeIII(aacac)Cl](ClO4)·1 mesitylene [aacac–=3-(9-anthryl)acetylacetonate(1–)], all of which have been characterized by X-ray crystallography. The magnetism, the Mössbauer-, EPR-, and UV-VIS-spectra and the electrochemistry of complexes are reported. 相似文献
14.
Marco H Klingele 《Inorganica chimica acta》2004,357(5):1598-1602
The synthesis and X-ray crystal structure of the complex {[CuII(Ph2PBPT)(bpy)](ClO4)2 · 2DMF}∞ where Ph2PBPT=4,4′-(1,4-phenylene)bis[3-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole], bpy=2,2′-bipyridine and DMF=N,N-dimethylformamide are reported. In this one-dimensional coordination polymer the Cu2+ ions are in a distorted octahedral N6 coordination environment made up of two Ph2PBPT molecules, each chelating via one pyridine and one triazole nitrogen, and one bpy co-ligand. Within the zig-zag chain thus formed the shortest distance between two metal centres across the Ph2PBPT ligand is 13.305(3) Å while it is 10.009(3) Å between two chains. This complex represents the first structurally characterised example of a coordination compound incorporating a chelating 4,4′-bis(4H-1,2,4-triazole) as a ligand. 相似文献
15.
The preparation and characterization of dichloro- (hydrotris(1-pyrazolyl)borato)pyridinechromium(III), CrCl2(HB(PYZ)3)Py, (Py = pyridine and HB(PYZ)3-1 is the hydrotris(1-pyrazolyl)borato anion) is described. The structure of the compound was determined by single crystal X-ray diffraction. Crystals were monoclinic, P21/c, a = 11.603(2), b = 9.845(1), c = 16.095(2) Å, β = 96.04(1)° with four formula units in the unit cell. Intensities were measured on a Nicolet P3 diffractometer with use of Mokα radiation. The structure was solved by standard methods and refined to R1 = 0.0601, R2 = 0.0397 based on 3142 independent reflections. Bond lengths and angles are normal. The pyridine molecule is oriented such that the plane bisects the angle between the two cis pyrazole rings. The synthesis and preparation of the related Cr(III) species CrCl2(HB(PYZ)3)pyrazole, Ph4As[CrCl3HB(PYZ)3] and [Cr(HB(PYZ)3)2]PF6 are described and the evaluation of the CrCl2(HB(PYZ)3)L (L = pyridine or pyrazole) species for genotoxicity is discussed. 相似文献
16.
Gangadhar B. Bagihalli Prema S. Badami 《Journal of enzyme inhibition and medicinal chemistry》2013,28(3):730-741
A series of metal complexes of La(III) and Th(IV) have been synthesized with newly derived biologically active ligands. These ligands were synthesized by the condensation of 3-substituted-4-amino-5-hydrazino-1,2,4-triazole with 8-formyl-7-hydroxy- 4-methylcoumarin. The structure of the complexes has been proposed by elemental analyses, spectroscopic data i.e. i.r., 1H nmr, Uv-Vis, FAB-mass and thermal studies. The elemental analyses of the complexes conform to the stoichiometry of the type [La(L)·3H2O]·2H2O and [Th(L)(NO3)·2H2O]·2H2O where (L = LI-LIV). All the complexes are soluble in DMF and DMSO and are non-electrolytes in DMF and DMSO. All these ligands and their complexes have also been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Staphylococcus pyogenes and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Aspergillus flavus and cladosporium) by the MIC method. The brine shrimp bioassay was also carried out to study their invitro cytotoxic properties. 相似文献
17.
《Inorganica chimica acta》1986,112(2):107-112
The synthesis and crystal and molecular structure of the first zinc(II) mixed ligand chelate containing a dithiolene ligand (maleonitriledithiolate) and N,N- diethyldithiocarbamate are reported. The compound Ph4As[Zn(mnt)(Et2dtc)] crystallizes monoclinic, space group P21/c with four molecules in the unit cell; a=17.834(3), b=12.056(2), c=16.171(4) Å, β=93.73(2)°.The coordination geometry of the ZnS4 unit is nearly tetrahedral, with a dihedral angle of 87.6° between the chelate rings. The structure is compared with those of both the patent compounds (Ph4- As)2[Zn(mnt)2] and Zn2(Et2dtc)4. Ph4As[Zn(mnt)(Et2dtc)] could be used as the host lattice in single- crystal ESR investigations of the planar Cu mixed ligand complex. The rhombic spin-Hamiltonian parameters g and ACu are indicative of a low symmetry of the incorporated [Cu(mnt)(Et2dtc)]− complex anions. In order to substantiate the experimental findings about the actual structure of the copper molecules, the principal values of g and ACu were recalculated by means of Extended Hückel MO calculations. However, the calculations performed for the dihedral angles between the ligand planes varying between 0° and 90° suggest that the rotation of the ligands is not larger than 10° 相似文献
18.
X. Do Thanh S. Djebbar-Sid S. Duchêne O. Benali-Baïtich G. Bouet M.A. Khan 《Biological Rhythm Research》2013,44(4):423-429
In vitro copper (II) complex presents antimitotic effects. In this work, we have studied the in vivo seasonal toxic effects of copper (II), ligand (H2L) and the complex [Cu(H2L)(H2O)2]Cl2·4H2O in male Swiss mice. During spring, an i.p. injection of CuCl2 in aqueous NaCl (9 g·l-1) up to 0.05 µmol·kg-1 b.w. (body weight) killed 60% of the rodents after 6 days. LD100 was up to 0.3 µmol·kg-1; H2L was well tolerated, while the complex was 30% lethal with 50 µmol·kg-1. In autumn, mice were less sensitive to CuCl2, and both ligand and complex were equally tolerated and this leads to the conclusion that, in vivo, chronotoxicities of copper (II) and complex in NaCl aqueous solutions are quite different in spring and autumn seasons. 相似文献
19.
《Inorganica chimica acta》2001,312(1-2):125-132
Di-organotin(IV)halides R2SnCl2 (R=Me or Ph) react with bis(diphenylphosphine)methane (DPPM) and bis(diphenylphosphine)ethane (DPPE) in ethanol in aerobic conditions yielding 1:1 adducts [R2SnCl2(DPPM–O2)] and [R2SnCl2(DPPE–O2)], respectively, containing the bis(diphenylphosphine) in oxidized form. The 1:1 adduct [SnMe2Cl2(DPPM–O2)] is composed of separate molecules containing six-coordinate tin, with the ligands coordinated in the bidentate O2-fashion, whereas [SnMe2Cl2(DPPE–O2)] is polymeric, with octahedral and centrosymmetric (all trans) tin atoms. In inert atmosphere, the interaction between R2SnCl2 and DPPM or DPPE does not take place. Mono-organotin halides RSnCl3 (R=Me, Bun or Ph) react with DPPM and DPPE yielding 1:1 adducts [RSnCl3(DPPM)] (R=Me, Bun or Ph) and [RSnCl3(DPPE)] (R=Bun or Ph). 相似文献
20.
《Journal of inorganic biochemistry》1991,41(2):79-85
A paramagnetic binuclear molybdenum(V) thioglycolate of composition Mo2(L)5(H2O)2 (H2L = CH2SHCOOH, thioglycolic acid) has been synthesized by direct reduction of molybdenum(VI) oxide hydrate (MoO3 · H2O) with thioglycolic acid in an argon atmosphere. Based on the combined results of elemental analysis, EPR, IR 1H NMR, electronic spectra, magnetic susceptibility, cyclic voltametry and x-ray photoelectron spectral measurements, it is concluded that in the title compound, both the molybdenum atoms are in pentavalent state with octahedral coordination through both sulphur and oxygen atoms of thioglycolic acid and water molecules. The two molybdenum ions have slightly different coordination environments due to bridging thioglycolate ions. 相似文献