共查询到20条相似文献,搜索用时 15 毫秒
1.
Umberto Belluco Roberta Bertani Rino A. Michelin Mirto Mozzon Franco Benetollo Gabriella Bombieri Robert J. Angelici 《Inorganica chimica acta》1995,240(1-2):567-574
The chloro complexes trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4, react with 1-alkynes HC---C---R in the presence of NEt3 to afford the corresponding acetylide derivatives trans-[Pt(Me) (C---C---R) (PPh3)2] (R = p-tolyl (1), Ph (2), C(CH3)3 (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH2)nCl (n = 2, 3) in the presence of 1 equiv. of HBF4 to afford the alkyl(chloroalkoxy)carbene complexes trans-[Pt(Me) {C[O(CH2)nCl](CH2R) } (PPh3)2][BF4] (R = p-tolyl, N = 2 (4), N = 3 (5); R=Ph, N = 2 (6)). A similar reaction of the bis(acetylide) complex trans-[Pt(C---C---Ph)2(PMe2Ph)2] with 2 equiv. HBF4 and 3-chloro-1-propanol affords trans-[Pt(C---CPh) {C(OCH2CH2CH2Cl)(CH2Ph) } (PMe2Ph)2][BF4] (7). T alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me) {C(OCH2CH2Cl)(CH2Ph) } (PPh3)2][BF4] (8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4 in HOCH2CH2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(μ-Cl)(PMe2Ph)]2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-[PtCl2{C(OCH2CH2CH2Cl)(CH2C6H4-p-Me}(PMe2Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna21, with a = 11.785(2), B = 29.418(4), C = 15.409(3) Å, V = 4889(1) Å3 and Z = 4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the Pt---C(carbene)---O moietry. 相似文献
2.
The X-ray structure is reported for the complex Cu2(medpco-2H)Cl2, (medpco = N,N′-bis-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. The complex is triclinic,
, a=8.313(4), B=11.403(5), C=11.611(3) Å, =91.66(3), β=108.99(4), γ=109.60(3)° and Z=2. The deprotonated ligand (medpco-2H)2− acts as a binulceating ligand, producing an N-oxide-bridged complex. Each copper in Cu2(medpco-2H)Cl2 is five-coordinate, being coordinated by a bridging N-oxide oxygen, a deprotonated amide nitrogen, a tertiary amine nitrogen and two bridging chlorides. The complex does not exhibit significant magnetic interaction, and this may be the result of distortion of the bridging geometry from planarity. A range of other, apparently N-oxide-bridged, complexes of the type Cu2(medpco-2H)X2 is reported. The complex Cu2(medpco-2H)Br2·H2O is strongly antiferromagnetic, with magnetic data closely fitting the expected binuclear structure. 相似文献
3.
Jean-Pierre Costes Franoise Dahan Jean-Pierre Laurent 《Inorganica chimica acta》1995,230(1-2):199-203
The ligand N, N′-bis[2,2-dimethyl-4-(2-hydroxyphenyl)-3-aza-3-buten] oxamide with two identical coordination sites reacts with copper ions in its tetradeprotonated form to yield the dinuclear complex [Cu2(C24H26N4O4)]·H2O. The structure of this compound has been determined by the X-ray diffraction method. The crystals are orthorhombic with a = 11.744(1), B = 16.369(2), C = 26.340(3) Å, V = 5064(1) Å3, Z = 8, space group Pbca. The oxamide is in a trans conformation with two different environments for the copper centres, a (4 + 1) coordination mode for the first one and a square planar environment for the other one. The water molecule is not directly bound to a copper centre, but involved in hydrogen bonding with the two oxygen atoms of an N2O2 coordination site. Indeed, extra coordination comes from a phenolic oxygen atom belonging to an adjacent dinuclear unit. Static susceptibility measurements point to a strong intrapair antiferromagnetic exchange interaction of 2J = −520(±4) cm−1 and possibly an interpair ferromagnetic exchange interaction of 10(±5) cm−1. 相似文献
4.
Olivier Horner Jean-Jacques Girerd Christian Philouze Luba Tchertanov 《Inorganica chimica acta》1999,290(2):8355-144
The new disymmetric ligand N,N,N′-tris(2-pyridylmethyl)-N′-(2-salicylideneethyl)ethane-1,2-diamine (LH) has been synthesized in the search of a novel type of manganese complex to mimic the active site of the water-oxidizing enzyme in photosystem II. The complex [Mn(II)L]ClO4 has been obtained and characterized by X-ray diffraction techniques. It crystallizes in the monoclinic space group Pn with the following unit cell parameters: a=10.164(3), b=10.122(4), c=14.166(5) Å, β=93.48(2)° and Z=2. The manganese ion is heptacoordinated with the coordination being achieved by only one ligand; it is bonded to the oxygen atom of the phenolate group in an axial position, the imino and the three pyridine nitrogen atoms in an equatorial position and the two amine atoms in a pseudo-axial position. The coordination polyhedron is best described as a distorted monocapped trigonal prism. This structure was compared with the seven-coordinated Mn(II) complexes deposited in the Cambridge Structured Database (CSD). The redox potential of the Mn(III)/Mn(II) couple was determined by cyclic voltammetry. 相似文献
5.
Two ruthenium(II) complexes with polypyridyl, Ru(bipy)2(phen)](ClO4)2·H2O (1) and [Ru(bipy)2(Me-phen)](ClO4)2 (2), (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, Me-phen = 5-methyl-1,10-phenanthroline), were synthesized and characterized by IR, MS and NMR spectra. Their structures were determined by single crystal X-ray diffraction techniques. The strong steric interaction between the polypyridyl ligands was relieved neither by the elongation of the Ru---N bonds nor increase of the N---Ru---N bite angles. The coordination sphere was distorted to relieve the ligand interaction by forming specific angles (δ) between the polypyridyl ligand planes and coordination planes (N---Ru---N), and forming larger twisted angles between the two pyridine rings for each bipy. The bond distances of Ru---N(bipy) and Ru---N(phen) were virtually identical with experimental error, as expected of π back-bonding interactions which statistically involve each of the ligands present in the coordination sphere. 相似文献
6.
Ademir Neves Cludio N. Verani Marcos A. de Brito Ivo Vencato Antnio Mangrich Glaucius Oliva Dulce D.H.F. Souza Alzir A. Batista 《Inorganica chimica acta》1999,290(2):2221-212
Copper(II) complexes were synthesized and characterized by means of elemental analysis, IR and visible spectroscopies, EPR and electrochemistry, as well as X-ray structure crystallography. The group consists of discrete mononuclear units with the general formula [Cu(II)(Hbpa)2](A)2·nH2O, where Hbpa=(2-hydroxybenzyl-2-pyridylmethyl)amine and A=ClO4 −, n=2 (1), CH3COO−, n=3 (2), NO3 −, n=2 (3) and SO4 2−, n=3 (4). The structures of the ligand Hbpa and complex 1 have been determined by X-ray crystallography. Complexes 1–4 have had their UV–Vis spectra measured in both MeCN and DMF. It was observed that the compounds interact with basic solvents, such that molecules coordinate to the metal in axial positions in which phenol oxygen atoms are coordinated in the protonated forms. The values were all less than 1000 M−1 cm−1. EPR measurements on powdered samples of 1–3 gave g/A values between 105 and 135 cm−1, typical for square planar coordination environments. Complex 4·3H2O exhibits a behaviour typical for tetrahedral coordination. The electrochemical behaviour for complexes 1 and 2 was studied showing irreversible redox waves for both compounds. 相似文献
7.
Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL1), 3,5-bis(2-pyridyl)pyrazole (HL2), 3-methyl-5-(2-pyridyl)pyrazole (HL3) and 3-methyl-5-phenylpyrazole (HL4) with [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) or [PdCl2(cod)] gives complexes with stoichiometry [PdCl2(HL)2] (HL = HL1, HL2, HL3), [Pt(L)2] (L = L1, L2, L3) and [MCl2(HL4)2] (M = Pd(II), Pt(II)). The new complexes were characterised by elemental analyses, conductivity measurements, infrared and 1H NMR spectroscopies. The crystal and molecular structure of [PdCl2(HL1)] was resolved by X-ray diffraction, and consists of monomeric cis-[PdCl2(HL1)] molecules. The palladium centre has a typical square planar geometry, with a slight tetrahedral distortion. The tetra-coordinated metal atom is bonded to one pyridine nitrogen, one pyrazolic nitrogen and two chloro ligands in a cis disposition. The ligand HL1 is not completely planar. 相似文献
8.
Elena Del Ministro Oliver Renn Heinz Rüegger Luigi M. Venanzi Urs Burckhardt Volker Gramlich 《Inorganica chimica acta》1995,240(1-2):631-639
Three seriesof Rh(I) complexes of the type Tp3R,5RRh(LL), with LL = 2 CO (1), norbornadiene (NBD) (2) and 1,5-cyclooctadiene (COD) (3) and the tris (pyrazolyl)borate (Tp) ligands 3R=5R=Me (a), 3R=CF35R=Me (b); and 3R=5R=CF3 (c) were synthesized and fully characterized by IR and multinuclear NMR spectroscopy. Three isomeric forms were identified in solutions of these complexes: two square-planar isomers with a κ2-Tp3R,5R ligand, the uncoordinated pyrazolyl ring occupying either an equatorial position (type A), or an axial position (type B), and a five-coordinate species with a κ3, Tp3R,5R ligand (type C). In the carbonyl complexes 1 the dynamic equilibria between these isomers are solvent dependent. Interestingly, solutions of complex 1c contained all three isomers simultaneously. 103Rh and 13C NMR spectral studies indicate that the NBD compounds, 2, preferentially form square-planar complexes when TpCF3,Me and TpCF3,CF3 are present, while for the COD complexes, 3, square-planar complexes are preferred for all three Tp-type ligands. The X-ray structure of TpCF3,MeRh(CO)2 (1b) was determined (spacce group C2/ c,a = 21.271(9), B = 11.004(3), C = 21.563(9) Å, β = 114.93(3)°, V=4577(3) Å3, Z = 8, R = 3.41, Rw = 4.70). Its structure is of type B, with the third pyrazolyl ring axially placed, the N(4) being almost directly above the Rh atom but exerting only a weak Rh-N interaction. 相似文献
9.
Gerard A van AlbadaIlpo Mutikainen Wilberth J.J SmeetsAnthony L Spek Urho TurpeinenJan Reedijk 《Inorganica chimica acta》2002,327(1):134-139
The synthesis, optical and magnetic properties and X-ray crystal structure of [Cu(2-aminopyrimidine)2(OH)(CF3SO3)]2(2-aminopyrimidine)2, a new dinuclear hydroxo-bridged copper(II) compound with a CuOCu angle of 97.96° and a very small antiferromagnetic interaction for which the singlet-triplet exchange parameter J, is described. The magnetic exchange coupling is almost negligible and, depending on the actual sample, varies from −1.8 to −7.2 cm−1. 相似文献
10.
Donato Monti Giuseppe Frachey Mauro Bassetti Anthony Haynes Glenn J. Sunley Peter M. Maitlis Andrea Cantoni Gabriele Bocelli 《Inorganica chimica acta》1995,240(1-2):485-493
The reactions of complex (C5Me5)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh2, PMePh2, PMe2Ph) give the products of alkyl migratory insertion (C5Me5Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C5Me5)Ir(Cl)(CO)(Ph) or the iodide complexes (C5Me5)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C5Me5)Ir(Cl)(CO)(Me) with PMePh2 and PMe2Ph in acetonitrile yields the chloride substitution product [(C5Me5)Ir(CO)(L)(Me)]+Cl−. Kinetic measurements for the reactions of (C5Me5)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C5Me5)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step (K = 1.5 (CyNC), 7.3 (PHPh2), 7.1 (PMePh2) dm3 mol−1 at 323 K) and k2 for the slow carbon---carbon bond formation (k2 (105) = 6.9 (CyNC), 1.2 (PHPh2), 1.0 (PMePh2) s−1 at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh2 obtained between 308 and 338 K, are ΔH≠ = 106±16 kJ mol−1 and ΔS≠ = − 14±5 J K−1 mol−1. The reaction of 1a with PMePh2 proceeds at similar rates in tetrahydrofuran (K = 3.7 dm3 mol−1, k2 (105) = 1.2 s−1, 323 K). The crystal structure of (C5Me5)Ir(Cl)(COMe) (PMe2Ph) has been determined by X-ray diffraction. C20H29ClOPIr: Mr = 544.1, monoclinic, P21/n, A = 8.084 (2), B = 9.030(2), C = 28.715 (3) Å, β = 91.41 (3)°, Z = 4, Dc = 1.71 g cm−3, V = 2095.5 Å3, room temperatyre, Mo K, γ = 0.71069, μ = 65.55 cm−1, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η5-C5Me5 molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the Ir---P and the Ir---COMe bonds are eclipsed with respect to C(ring)-methyl bonds. 相似文献
11.
C Valan AmburoseTheivanayagam C Deivaraj Ghee Xiong LaiJeyagowry T Sampanthar Jagadese J Vittal 《Inorganica chimica acta》2002,332(1):160-166
We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me)nCl4−n]2− (n=3, 4) and [Cd2Cl2(SC{O}Me)4]2−. Complexes of the formula [Ph4P]2[M(SC{O}Me)4] (M=Zn(II) (1), Cd(II) (2) or Hg(II) (3)) were synthesized by the reaction of thioacetate ligand with the metal salts and Ph4PCl in 4:1:2 molar ratio in suitable solvents. The geometry of Zn(II) in 1 is nearly tetrahedral and the distortion in tetrahedron increases in the order of 1<2<3 as observed from the SMS angles in the crystal structures. The tendency of monoanionic complexes [Ph4P][M(SC{O}Me)3] to react with 1 mole equivalent of Ph4PCl resulted in complexes of the type [Ph4P]2[M(SC{O}Me)3Cl] (M=Cd(II) (4) or Hg(II) (5)). In the structures of 4 and 5, three sulfur atoms and one chloride atom occupy the corners of the tetrahedron around the metal centers. However, in a 4:2:2 or 2:1:2 molar reaction of Me{O}CS− with CdCl2 and Ph4PCl in aqueous medium resulted in a chloro bridged dimer, [Ph4P]2[Cd2(μ-Cl)2(SC{O}Me)4] (6) as determined by X-ray crystallography. 相似文献
12.
Jeffrey P. Flemming Mark C. Pilon Oleg Ya. Borbulevitch Mikhail Yu. Antipin Vladimir V. Grushin 《Inorganica chimica acta》1998,280(1-2):87-98
Single crystal X-ray diffraction studies of trans-[(Ph3P)2Pd(Ph)X] (X = F (1), Cl (2), Br (3), and I (4) were carried out. The four structures split in two isostructural and isomorphous groups, namely orthorhombic for 1 and 2 (space group Pbca, Z = 8) and triclinic for 3 and 4 (space group P-1, Z = 2). According to the Pd---C bond length, the trans influence of X within these pairs follows the trend Cl>F and 1>Br. However, the trans influence of Cl is slightly stronger than that of Br. Both structural and 13C NMR studies revealed that electron-donating effects of (Ph3P)2PdX increase along the series X=I
− for the Pd centre in [(Ph3P)2Pd(Ph)]− were studied by 31P NMR in rigorously anhydrous CH2Cl2 solutions, and equilibrium constants and ΔG values were obtained for all possible combinations. The sequence F− > Cl− > Br− > I− is characteristic of halide preference for the Pd complexes. Dissolving 1 and PPN Cl in dry CH2Cl2 resulted in the release of ‘naked’ F− which fluorinated the solvent smoothly to give a mixture of CH2ClF and CH2F2 in high yield. When chloroform was used instead of CH2Cl2, dichlorocarbene was generated slowly, forming the corresponding cyclopropane in the presence of styrene. All observations were rationalized successfully in terms of the filled/filled effect and push/pull interactions. 相似文献
− for the Pd centre in [(Ph3P)2Pd(Ph)]− were studied by 31P NMR in rigorously anhydrous CH2Cl2 solutions, and equilibrium constants and ΔG values were obtained for all possible combinations. The sequence F− > Cl− > Br− > I− is characteristic of halide preference for the Pd complexes. Dissolving 1 and PPN Cl in dry CH2Cl2 resulted in the release of ‘naked’ F− which fluorinated the solvent smoothly to give a mixture of CH2ClF and CH2F2 in high yield. When chloroform was used instead of CH2Cl2, dichlorocarbene was generated slowly, forming the corresponding cyclopropane in the presence of styrene. All observations were rationalized successfully in terms of the filled/filled effect and push/pull interactions. 相似文献
13.
Oleg V. Gusev Mikhail A. Ievlev Konstantin A. Lyssenko Pavel V. Petrovskii Nikolai A. Ustynyuk Peter M. Maitlis 《Inorganica chimica acta》1998,280(1-2):249-256
The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru2(η5-C5Me1CF2)2 (μ-Cl2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2J=200 cm1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh2(η5-C5Me4CF3(2Cl2(μ-Cl)2] (3) (rhombohedral system.
space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η5-C5Me4CF4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2(μ-Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the η5-C5ME5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2(η5-C5Me4CF3)2Br2 (μ-Br2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric η6-fulvene dimers [Ru2(η6-C5Me3CF3 = CH2)2Cl2(μ-Cl)2] (5). Reactions of 5 with CO and allyl chloride give Ru(η5-C5Me3CF3CH2Cl)(CO)2Cl (6) and Ru(η5-C5Me3CF3CF3CH2Cl)(η3-C3H5)Cl2 (7) respectively. 相似文献
14.
Barbara del Klerk-Engels Jos G. P. Delis Jan-Meine Ernsting Cornelis J. Elsevier Hans-Werner Frü hauf Derk J. Stufkens Kees Vrieze Kees Goubitz Jan Fraanje 《Inorganica chimica acta》1995,240(1-2):273-284
Reaction of RuCl(η5-C5H5(pTol-DAB) with AgOTf (OTf = CF3SO3) in CH2Cl2 or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η5-C5H5)(pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η5-C5H5)(pTol-DAB)(fumarontrile-N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η5-C5H5)(pTol-DAB)(η2-ethene)][CF3SO3] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P21/n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) Å3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η5-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η2-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η5-C5H5)(PPh)3 with AgOTf and ligands L′ = a and d led to [Ru(η5-C5H5)(PPh3)2(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η5-C5H5)(L2)(η2-alkene][OTf] with L2 = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh3 (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol−1, respectively. The intermediate exchange could not be reached for 1c, and the ΔG# was estimated to be at least 61 kJ mol−. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol−. The rotational barier for methyl propiolate (HC≡CC(O)OCH3) (k) in complex [Ru(η5-C5H5)(iPr-DAB) η2-HC≡CC(O)OCH3)][OTf] (1k) is 45.3±0.2 kJ mol−1. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state. 相似文献
15.
Giovanni De Munno Miguel Julve Jos Antonio Real Francesc Lloret Rosario Scopelliti 《Inorganica chimica acta》1996,250(1-2):81-85
The iron(II) compound of formula [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the tetragonal P41 (No. 76) and P43 space groups, a = 8.849(2), C=16.486(3) Å, V=1290.9(5) Å3, Z=4, Dc=1.699 g cm−3, Mr=330.2, F(000)=664, λ(Mo K)=0.71073 Å, μ(Mo K)=14.8 cm−1 and T=295 K. A total of 2449 reflections was collected over the range 3≤2≤55°; of these, 1657 were unique and 1321 were considered as observed (13σ(I)) and used in the structural analysis. The final R and Rw residuals were 0.027 and 0.026, respectively. The structure is made up of chiral (Δ and Λ enantiomers crystallize in the same crop) chains of iron(II) atoms bridged by bis-chelating bpym, the electroneutrality being achieved by N-bonded thiocyanato groups in cis position. Each metal atom is in a distorted FeN6 octahedral environment, the Fe---N bonds ranging from 2.265(3) to 2.028(4)
. The intrachain metal-metal separation is 5.960(1) Å. Variable-temperature magnetic susceptibility data in the temperatyre range 290–4.2 K show that the iron(II) is high-spin and interacts in an antiferromagnetic fashion, the relevant parameters being . The magnitude of the exchange coupling compares well with that reported for other structurally characterized bpym-bridged iron(II) complexes. 相似文献
16.
Fabiola Estudiante-Negrete Simón Hernández-Ortega David Morales-Morales 《Inorganica chimica acta》2007,360(5):1651-1660
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.
Mohammad Akbar Ali Aminul Huq Mirza Ray J. Butcher M. T. H. Tarafder Manaf A. Ali 《Inorganica chimica acta》2001,320(1-2):1-6
The Schiff base formed by condensation of 2,6-diacetylpyridine with S-benzyldithiocarbazate (H2SNNNS) behaves as a pentadentate ligand, forming a nickel(II) complex of empirical formula Ni(SNNNS)·H2O that is high-spin with a room-temperature magnetic moment of 2.93 B.M. Spectroscopic data indicate that the ligand coordinates with the nickel(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. The crystal and molecular structure of the nickel(II) complex was determined by X-ray crystallography. The complex crystallizes in the monoclinic system, space group C2/c, with a=15.849(2), b=18.830(2) and c=18.447(2) Å and =90°, β=102.179(6)°, γ=90° and Z=8. The crystal structure analysis shows that the complex is dinuclear, [Ni(SNNNS)]2·2H2O, in which the nickel(II) ions are bridged by the two pyridine nitrogen atoms of two fully deprotonated ligands. The NiN4S2 coordination geometry about each nickel(II) ion can be described as a distorted octahedron. The Schiff base and its nickel(II) complex were tested against four pathogenic bacteria (Bacillus subtilis, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus and B. subtilis (wild type B29) and pathogenic fungi (Saccharomyces ceciricae, Candida albicans, Candida lypolitica and Aspergillus ochraceous) to assess their antimicrobial properties. Both compounds exhibit mild antibacterial and antifungal activities against these organisms. The anticancer properties of these compounds were also evaluated against Human T-lymphoblastic leukaemia cell lines. The Schiff base exhibits marked cytotoxicity against these cells, but its nickel(II) complex is inactive. 相似文献
18.
The reactions of [(H5C6)3P]2ReH6− with (CH3CN)3Cr(CO)3, (diglyme)Mo(CO)3 or (C3H7CN)3W(CO)3 led to the formation of [(H5C6)3P]2ReH6M(CO)3− (M = Cr, Mo, W) complexes. These have been characterized by IR and NMR spectroscopies, as well as elemental analyses. A single crystal X-ray diffraction study has also been carried out for the M = Cr complex as a K(18-crown-6)+ salt. The complex crystallizes as a THF monosolvate in the monoclinic space group P21/n with a = 22.323(6), B = 9.523(2), C = 27.502(5) Å, β = 104.98(2)0 and V = 5648 Å3 for Z = 4. The Re---Cr separation is 2.5745(12) Å, and the two phosphine ligands are oriented unsymmetrically. Although the hydride ligands were not found, the presence of three bridging hydrides and a dodecahedral coordination geometry about rhenium could be inferred. Low temperature 1H and 31P NMR spectroscopic studies did not reveal the low symmetry of the solid state structure. 相似文献
19.
The ligand 1,4,7-triazacyclononane-1,4,7-tris[2′(R)-2′-propionate](-3)((R)-tacntp3−), binds stereospecifically to transition metal ions. The structures of the complexes [Cr((R)-tacntp)]·NaBr and [Fe((R)-tacntp)]·H2O have been determined by X-ray crystallography. Both complexes have the Λ-configuration but the conformation of the chelate rings in Λ-[Cr((R)-tacntp)] is (λ,λ,λ) with a geometry close to octahedral while in Λ-[Fe((R)-tacntp)] it is (δ,δ,δ) and the geometry is closer to that of a trigonal prism. Chiral induction in the electron transfer reactions of Λ-[Co((R)-tacntp)], Λ-[Fe((R)-tacntp)] and Λ-[Mn((R)-tacntp)] with [Co((RR,SS)-chxn)3]2+ has been investigated. All three reactions are outer-sphere and four isomeric [Co((RR,SS)-chxn)3]3+ products are identified in each case. The oxidants Λ-[Fe((R)-tacntp)] and Λ-[Mn((R)-tacntp)] show very similar selectivities, quite different from those of Λ-[Co((R)-tacntp)]. Reasons for this behavior are discussed. 相似文献
20.
Two novel complexes, Cd(HTMA)(NC5H5)2 · 0.5CH3OH · 0.5DMF (1) and Cd(HTMA) · 2H2O (2), of cadmium (II)-trimesates are obtained from slow vapor diffusion and urea hydrolysis, respectively. The Cd(II) centers in the two complexes are bridged by three separate HTMA3− ligands using a same coordination fashion, which contains one monodentate and two chelating bidentate carboxyl groups to form the herringbone-like motif. The herringbone-like motif is further interlinked to construct the two-dimensional Cd(II)-HTMA layer, which is stacked by mutual π-stacking of pyridines for 1 and by hydrogen bond of waters for 2. Thermal stabilities of the two complexes were investigated and the results indicated that Cd(II)-TMA layers in the two complexes are stable still upon 190 °C. 相似文献