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1.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4.  相似文献   

2.
The reaction of TiCl4 with Li2[(SiMe2)25-C5H3)2] in toluene at room temperature afforded a mixture of cis- and trans-[(TiCl3)2{(SiMe2)25-C5H3)2}] in a molar ratio of 1/2 after recrystallization. The complex trans-[(TiCl3)2{(SiMe2)25-C5H3)2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-[(TiCl2)2(μ-O){(SiMe2)25-C5H3)2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-[(TiCl3)2{(SiMe2)25-C5H3)2}] under different conditions led to the dinuclear μ-oxo complex cis-[(TiCl2)2)(μ-O){(SiMe2)25-C5H3)2}] and two oxo complexes of the same stoichiometry [(TiCl)2(μ-O){(SiMe2)25-C5H3)2}]2(μ-O)2 as crystalline solids. Alkylation of cis- and trans-[(TiCl3)2{(SiMe2)25-C5H3)2}] with MgCIMe led respectively to the partially alkylated cis-[(TiMe2Cl)2{(SiMe2)25-C5H3)2}] and the totally alkylated trans-[(TiMe3)2{(SiMe2)25-C5H3)2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex [(TiCl)2(μ-O){(SiMe2)25-C5H3)2}]2(μ-O)2 was determined by X-ray diffraction.  相似文献   

3.
The hydrothermal reactions of (Ph4P)[VO2Cl2] and H2C2O4 at 150 and 125°C yield (Ph4P)2[V2O2(H2O)2(C2O4)3]·4H2O (1) and (Ph4P)[VOCl(C2O4)] (2), respectively. The structure of the molecular anion of 1 consists of a binuclear unit of oxovanadium(IV) octahedra bridged by a bisbidentate oxalate group. The VO6 coordination geometry at each vanadium site is defined by a terminal oxo group, an aquo ligand, and four oxygen donors — two from the bisbidentate bridging oxalate and two from the terminal bidentate oxalate. The structure of 2 consists of discrete Ph4P+ cations occupying regions between [VOCl(C2O4)] spiral chains. The structure of the one-dimensional anionic chain exhibits V(IV) octahedra bridged by bisbidentate oxalate groups. Crystal data: 1·4H2O, monoclinic P21/n, A = 12.694(3), B = 12.531(3), C = 17.17(3) Å, β = 106.32(2)°, V = 2621.3(13) Å3, Z = 2, Dcalc = 1.501 g cm−3, structure solution and refinement converged at a conventional residual of 0.0518; 2, tetragonal P43, A = 12.145(2), C = 15.991(3) Å, V = 2358.7(12) Å3, Z = 4, R = 0.0452.  相似文献   

4.
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   

5.
The reactions of the polysulfur and selenium cationic clusters S82+ and Se82+ with various iron carbonyls were investigated. Several new chalcogen containing iron carbonyl cluster cations were isolated, depending on the nature of the counteranion. In the presence of SbF6 as a counterion, the cluster [Fe3(E2)2(CO)10] [SbF6]2·SO2 (E = S, Se) could be isolated from the reaction of E82+ and excess iron carbonyl. The cluster is a picnic-basket shaped molecule of two iron centers linked by two Se2 groups, with the whole fragment capped by an Fe(CO)4 group. Crystallographic data for C10O12Fe3Se4Sb2F12S (I): space group monoclinic P21/c, A = 11.810(9), b = 24.023(6), c = 10.853(7) Å, β = 107.15(5)°, V = 2942(3) Å3, Z = 4, R = 0.0426, Rw = 0.0503. When Sb2F11 is present as the counterion, or Se4[Sb2F11]2 is used as the cluster cation source, a different cluster can be isolated, which has the formula [Fe4(Se2)3(CO)12] [SbF6]2·3SO2. The dication contains two Fe2Se2 fragments bridged by an Se2 group. Crystallographic data for C12O18Fe4Se6Sb2F12S3 (III): space group triclinic , b = 18.400(9), C = 10.253(4) Å, = 93.10(4), β = 103.74(3), γ = 93.98(3)°, V = 1995(1) Å3, Z = 2, R = 0.0328, Rw = 0.0325. The CO stretches in the IR spectrum all show a large shift to higher wavenumbers, suggesting almost no τ backbonding from the metals. This also correlates with the observed bond distances. All the compounds are extremely sensitive to air and water, and readily lose SO2 when removed from the solvent. Thus all the crystals were handled at −100°C. The clusters seem to be either insoluble or unstable in all solvents investigated.  相似文献   

6.
The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru25-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 [Rh25-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 [Ru25-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 [Ru26-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   

7.
A series of cuboidal iron-sulfur clusters [Fe4S3(NO)4(PR3)3]0,1+ (R = Et, Pri, Cy) were synthesized by two routes: reductive desulfurization of [Fe4S4(NO)4] by tertiary phosphines, and substitution of triphenylphosphine in [Fe44S3(NO)4(PPh3)3] by a more basic phosphine. The structures of 3[Fe4S3(NO)4(PEt3)3] · 0.5Et2O, [Fe4S3(NO)4(PEt3)3] [Fe4S3(NO)7] and partially substituted [Fe4S3(NO)4(PPh3)2 (PPri3)] have been determined by X-ray diffraction in order to define the cuboidal Fe4S3 core, previously known only in Roussin's black anion and its reduced form, [Fe4S3(NO)77]1−,2−, and as a part of the iron-molybdenum cofactor of nitrogenase.  相似文献   

8.
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   

9.
The trinuclear clusters [Pd3(μ-dppm)3(CO)]2+ and [PtPdCo(μ-dppm)2(CO)3(CNtBu)]+ exhibit a large and a small cavity, respectively, formed by the phenyl rings of the bridging diphosphine ligands. Their binding constants (K11) with halide ions (X) were obtained by UV-Vis spectroscopy. The binding ability varies as I > Br > Cl, and [Pd3(μ-dppm)3(CO)]2+ > [ptPdCo(μ-dppm)2-(CO)3(CNtBu)]+. The MO diagram for the related cluster [Pd2Co(μ-dppm)2(CO)4]+ has been addressed theoretically in order to predict the nature of the lowest energy electronic bands. For this class of compounds, the lowest energy bands are assigned to charge transfers from the Co center to the Pd2 centers.  相似文献   

10.
The labile cations [Cu(F-BF3)(PCy3)2] and [Cu(OTf)(PCy3)2] are versatile precursors for the formation of [Cu(X)(PCy3)2] (X = Br, I, SCN, N3) complexes by metathesis with NaX. The azide [Cu(N3)(PCy3)2] is triclinic, space group , a = 9.755(4), B = 22.78(1), C = 9.284(6) Å, = 96.76(3), β = 115.36(3), γ = 94.20(5)°, Z = 2.  相似文献   

11.
The reaction of [N(PPh3)2]2[Ni6(CO)12] with Cu(PPh3)xCl (x=1, 2), as well as the degradation of [N(PPh3)2]2[H2Ni12(CO)21] with PPh3, affords the new and unstable dark orange–brown [N(PPh3)2]2[Ni9(CO)16].THF salt in low yields. This salt has been characterized by a CCD X-ray diffraction determination, along with IR spectroscopy and elemental analysis. The close-packed two-layer metal core geometry of the [Ni9(CO)16]2− dianion is directly related to that of the bimetallic [Ni6Rh3(CO)17]3− trianion and may be envisioned to be formally derived from the hcp three-layer geometry of [Ni12(CO)21]4− by the substitution of one of the two outer [Ni3(CO)3(μ−CO)3]2− layers with a face-bridging carbonyl group.  相似文献   

12.
New manganese(III) complexes of Hphox (2-(2′-hydroxyphenyl)-oxazoline) and HClphox (2-(5′-chloro-2′-hydroxyphenyl)-oxazoline) have been synthesised. The X-ray structures of [Mn(phox)2(MeOH)2][Mn(phox)2(ClO4)2](H2O)2 and [Mn(Clphox)2(MeOH)2](ClO4) show the manganese(III) ions to be octahedrally coordinated with methanol or perchlorate at the axial coordination sites. The cyclic voltammograms of the complexes, with the exception of [Mn(phox)2(acac)] (Hacac=2,4-pentanedione), show an irreversible reduction wave of manganese(III) to manganese(II). After addition of an excess of 1-methylimidazole (1-Meim), the reduction process shifts towards lower potentials and becomes (quasi-) reversible, indicating that the presence of 1-Meim affects the catalytic efficiency of the complexes. The complexes catalyse the epoxidation of styrene by dihydrogen peroxide. The cumulative turnover numbers towards styrene oxide obtained after 15 min. vary from 16 for [Mn(Clphox)2(MeOH)2](ClO4) to 26 for [Mn(phox)2(acac)]. Ligand degradation appears to be the limiting factor for obtaining higher turnover numbers.  相似文献   

13.
A novel five-coordinate rhenium(III)-thiolato complex, Re(SCH2C6H4OCH3-p)3(PPh3)2 has been isolated during the reaction of trans-ReOCl3(PPh3)2 with p-methoxybenzyl mercaptan. In the unexpected structure that was acquired, the central metal has undergone a reduction from Re(V) to Re(III). The five-coordinate Re(III) complex has been characterized by spectroscopic methods, elemental analysis and X-ray crystallography. X-ray crystallographic studies showed the coordination geometry around rhenium to be that of a trigonal bipyramid. The basal plane is defined by three sulfur atoms of the monodentate ligand, while the two apical positions are occupied by two phosphines of the precursor.  相似文献   

14.
Compounds of formula [Al(CH3CN)6][MCl6]3(CH3CN)3 (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl5 and AlCl3 in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) Å3 and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330(a), C = 15.320(3) Å3 V = 1634.8(4) Å3 and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) Å3 and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation.  相似文献   

15.
The preparation and structural characterization of {Ru3(CO)11}2(1,4-bis(diphenylphosphino)benzene), a modified synthesis of 1,4-bis(diphenylphosphino)benzene, and the structural characterization of {Ru3(CO)11}2(bis(diphenylphosphino)ethane) are reported. In both compounds two metal cluster units are connected through ditertiary-phosphine ligands. Both molecules consist of centrosymmetric units in which the diphosphine ligands are largely covered by the triangular ruthenium clusters. No direct interaction between the two cluster units occurs within individual molecules. Molecular packing in the solid state is dominated by interactions between sets of carbon monoxide ligands in motifs that were previously identified in the solid state structure of the parent cluster, Ru3(CO)12.  相似文献   

16.
With exposure to trace amounts of air and moisture, the Cr2(II, II) complex Cr2(μ-3,5Cl2-form)4, where 3,5Cl2-form is [(3,5-Cl2C6H3)NC(H)N(3,5-Cl2C6H3)], undergoes an oxidative addition reaction. Structural information from the X-ray crystal structure of the edge-sharing bioctahedral (ESBO) Cr2(III, III) product Cr2(μ-OH)2(μ-3,5Cl2-form)22-3,5Cl2-form)2 (1) indicates 1 has a significantly longer Cr–Cr distance [2.732(2) Å] than Cr2(μ-3,5Cl2-form)4 [1.9162(10) Å], but the shortest Cr–Cr distance in an ESBO Cr2(III, III) complex recorded to date.  相似文献   

17.
Reactions of [Rh(COD)Cl]2 with the ligand RN(PX2)2 (1: R = C6H5; X = OC6H5) give mono- or disubstituted complexes of the type [Rh2(COD)Cl22−C6H5N(P(OC6H5)2)2}] or [RhCl{ν2−C6H5 N(P(OC6H5)2)2 }]2 depending on the reaction conditions. Reaction of 1 with [Rh(CO)2Cl]2 gives the symmetric binuclear complex, [Rh(CO)Cl{μ−C6H5N(P(OC6H5)2)2} 2, whereas the same reaction with 2 (R = CH3; X = OC6H5) leads to the formation of an asymmetric complex of the type [Rh(CO)(μ−CO)Cl{μ−CH3N(P(OC6H5)2)2}2 containing both terminal and bridging CO groups. Interestingly the reaction of 3 (R = C6H5, X = OC6H4Br−p with either [Rh(COD)Cl]2 or [Rh(CO)2Cl]2 leads only to the formation of the chlorine bridged binuclear complex, [RhCl{ν2−C6H5N(P(OC6H4Br−p)2)2}]2. The structural elucidation of the complexes was carried out by elemental analyses, IR and 31P NMR spectroscopic data.  相似文献   

18.
The enthalpies of reaction of HMo(CO)3C5R5 (R = H, CH3) with diphenyldisulfide producing PhSMo(CO)3C5R5 and PhSH have been measured in toluene and THF solution (R = H, ΔH= −8.5 ± 0.5 kcal mol−1 (tol), −10.8 ± 0.7 kcal mol−1 (THF); R = CH3, ΔH = −11.3±0.3 kcal mol−1 (tol), −13.2±0.7 kcal mol−1 (THF)). These data are used to estimate the Mo---SPh bond strength to be on the order of 38–41 kcal mol−1 for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)3Cp yielding [PhSMo(CO)2Cp]2 and [PhSMo(CO)Cp]2. The enthalpies of reaction of PhSMo(CO)3Cp and [PhSMo(CO)2Cp]2 with PPh3, PPh2Me and P(OMe)3 have also been measured. The disproportionation reaction: 2[PhSMo(CO)2Cp]2 → 2PhSMo(CO)3Cp + [PhSMP(CO)Cp]2 is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)nC5H5]2, N = 1,2.  相似文献   

19.
Two new spin-crossover complexes, [Fe(Medpq)(py)2(NCS)2] · py · 0.5H2O (1) and [Fe(Medpq)(py)2(NCSe)2] · py (2) (Medpq = 2-methyldipyrido[3,2-f:2′,3′-h]-quinoxaline, py = pyridine), have been synthesized. The crystal structures were determined at both room temperature (298 K) and low temperature (110 K). Complexes 1 and 2 crystallize in the orthorhombic space group Pbca and monoclinic space group P21/n, respectively. In both complexes, the distorted [FeN6] octahedron is formed by six nitrogen atoms from Medpq, the trans pyridine molecules and the cis NCX groups. The thermal spin transition is accompanied by the shortening of the mean Fe–N distances by 0.194 Å for 2. The mononuclear [Fe(Medpq)(py)2(NCS)2] and [Fe(Medpq)(py)2(NCSe)2] neutral species interact each other via π-stacking, resulting in a one-dimensional extended structure for both 1 and 2. There exist C–HX (X = S, Se) hydrogen bonds for both complexes. Variable-temperature magnetic susceptibility measurements and Mössbauer spectroscopy reveal the occurrence of a gradual spin transition. The transitions are centered at T1/2 = 120 K for 1 and T1/2 = 180 K for 2, respectively.  相似文献   

20.
Four complexes of the type [Cu4I4(CH3CN)2(L)2], L = aniline derivative: Cu4I4(CH3CN)2(2,6-dimethylaniline)2 (I), triclinic, , a = 12.449(3), B = 14.108(6), C = 10.606(4) Å, = 73.46(3), β = 95.00(2), γ = 73.42(3)°, V = 1682.3(10) Å3; Cu4I4(CH3CN)2(o-ethylaniline)2 (II), triclinic, , V = 1734.0(8) Å3; Cu4I4(CH3CN)2(6-ethyl-o-toluidine)2 (III), orthorhombic, Pnam, a = 14.976(6), b = 21.187(6), C = 12.545(2) Å, V = 3980.7(2) Å3; Cu4I4(CH3CN)2(p-anisidine)2 (IV), monoclinic, A2/a, A = 20.032(10), B = 7.863(1), C = 18.715(9) Å, β = 101.56(4)°, V = 2888.0(2) Å3; were examined by single crystal X-ray diffraction. Complexes I and II have no internal symmetry elements, III has an internal mirror and IV has a two-fold axis. Ab initio calculations based on the atomic positional parameters of complexes containing the three types of symmetry elements reveal HOMO orbitals to be dominated by the p orbitals of the iodine atoms whereas the LUMO orbitals contain major contributions from copper based p orbitals.  相似文献   

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