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1.
A new complex [Cu (C 4H 7N 3) H 2O (4,4′-Hbpy)]·SO 4·NO 3 was synthesized and X-ray characterized. Elemental analysis, X-ray diffraction and infrared spectroscopy of the complex were performed. The crystal system is orthorhombic. Crystal data: Fw=498.98, spacegroup: P212121. Z=4, a=14.952(3), b=20.491(4), c=6.713 Å. V=2056.7(9) Å. λ(Mo-K)=0.71070 Å. μ=12.18 cm −1, Dcalc=1.66 g/cm 3, F000=1032.00, R=0.062, Rw=0.087. X-ray analysis illustrated that 4,4′-bpy is mono-protonated and that there are two kinds of anions in one molecule, which give rise to the hydrogen interaction between the molecules in the crystal. Then an extended three-dimensional network is formed along the hydrogen bonds and π–π bonds between the pyridine rings. 相似文献
2.
The triplet state ( 32T) and the radical cation (2T +√) of 2,2′-bithiophene (2T) are characterized by pulse radiolysis in CCl 4. Two main absorption bands at 360 and 420 nm are respectively attributed to 32T* and to 2T +√. The triplet, induced in an excited state through a Förster mechanism, undergoes a conformational rearrangement ( k6=(6.8±0.9)×10 6 s −1). The radical cation is produced both through a resonance charge transfer and a second diffusional process; the two oxidizing species are respectively CCl 4+√ and (CCl +3Cl −) solv through the mediation of a singlet excited state, 12T*. 相似文献
3.
The reactions of the diruthenium carbonyl complexes [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)]X (X=BF 4− (1a) or PF 6− (1b)) with neutral or anionic bidentate ligands (L,L) afford a series of the diruthenium bridging carbonyl complexes [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-(L,L)) 2]X n ((L,L)=acetate (O 2CMe), 2,2′-bipyridine (bpy), acetylacetonate (acac), 8-quinolinolate (quin); n=0, 1, 2). Apparently with coordination of the bidentate ligands, the bound acetate ligand of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + either migrates within the same complex or into a different one, or is simply replaced. The reaction of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + (1) with 2,2′-bipyridine produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe) 2] (2), [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-bpy)] + (3), and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-bpy) 2] 2+ (4). Alternatively compound 2 can be prepared from the reaction of 1a with MeCO 2H–Et 3N, while compound 4 can be obtained from the reaction of 3 with bpy. The reaction of 1b with acetylacetone–Et 3N produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-acac)] (5) and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-acac) 2] (6). Compound 2 can also react with acetylacetone–Et 3N to produce 6. Surprisingly [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-quin) 2] (7) was obtained stereospecifically as the only one product from the reaction of 1b with 8-quinolinol–Et 3N. The structure of 7 has been established by X-ray crystallography and found to adopt a cis geometry. Further, the stereospecific reaction is probably caused by the second-sphere π–π face-to-face stacking interactions between the phenyl rings of dppm and the electron-deficient six-membered ring moiety of the bound quinolinate (i.e. the N-included six-membered ring) in 7. The presence of such interactions is indeed supported by an observed charge-transfer band in a UV–vis spectrum. 相似文献
4.
A series of Ce xPr 1−xO 2−δ mixed oxides were synthesized by a sol–gel method and characterized by Raman, XRD and TPR techniques. The oxidation activity for CO, CH 3OH and CH 4 on these mixed oxides was investigated. When the value x was changed from 1.0 to 0.8, only a cubic phase CeO 2 was observed. The samples were greatly crystallized in the range of the value x from 0.99 to 0.80, which is due to the formation of solid solutions caused by the complete insertion of Pr into the CeO 2 crystal lattices. Raman bands at 465 and 1150 cm −1 in Ce xPr 1−xO 2−δ samples are attributed to the Raman active F 2g mode of CeO 2. The broad band at around 570 cm −1 in the region of 0.3 ≤ x ≤ 0.99 can be linked to oxygen vacancies. The new band at 195 cm −1 may be ascribed to the asymmetric vibration caused by the formation of oxygen vacancies. The TPR profile of Pr 6O 11 shows two reduction peaks and the reduction process is followed: . The reduction temperature of Ce xPr 1−xO 2−δ mixed oxides is lower than those of Pr 6O 11 or CeO 2. TPR results indicate that Ce xPr 1−xO 2−δ mixed oxides have higher redox properties because of the formation of Ce xPr 1−xO 2−δ solid solutions. The presence of the oxygen vacancies favors CO and CH 3OH oxidation, while the activity of CH 4 oxidation is mostly related to reduction temperatures and redox properties. 相似文献
5.
With a hydrothermal technique, a layered titanium phosphate with the formula Ti 2(H 2PO 4)(HPO 4)(PO 4) 2 · 0.5C 6N 2H 16 (denoted TP-J2) has been prepared by treating the Ti/H 3PO 4/H 2O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state 31P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å. = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine ( n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N, N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip. 相似文献
6.
Reaction of [18]aneS 6 with two molar equivalents of [Cu(NCMe) 4](ClO 4) in CH 2Cl 2-MeCN affords the binuclear copper(I) complex [Cu 2([18]aneS 6)(NCMe) 2](ClO 4) 2. The single crystal X-ray structure of the complex shows a centrosymmetric cation with two tetrahedral copper(I) centres each coordinated to three thioether S-donors of [18]aneS 6,Cu---S(1) = 2.3200(15), Cu---S(4) = 2.3415(16), Cu---S(7) = 2.3250(15) Å, and to one MeCN molecule, Cu---N(1) = 1.939(5) Å, to give an overall NS 3-donation at the metal centres. Additionally, S(7′) shows a long-range interaction, Cu …S(7′) = 3.318(2) Å thus distorting the coordination geometry of the metal ion towards trigonal bipyramidal. The metal-metal separation of 4.428(2) Å suggests that there is no significant interaction between the copper centres of the dimer. Reaction of [9]aneS 3 with one molar equivalent of [Cu(NCMe) 4](ClO 4) in refluxing MeCN in the presence of ligands, L, affords the adducts [Cu([9]aneS 3)L] + (L = PPh 3, AsPh 3). The single crystal X-ray structure of the complex [Cu([9]aneS 3)(AsPh 3)](ClO 4) shows tetrahedral AsS 3 coordination at copper(I) with [9]aneS 3 bound facially to the metal centre, Cu---S = 2.303(6), Cu---As = 2.322(4) Å. 相似文献
7.
The hydrogen bond strength in kieserite-type sulfate and selenate monohydrates has been studied by the method of double-matrix spectroscopy. The infrared spectra of isotopically dilute (matrix-isolated HDO molecules) kieserite-type compounds MXO 4·H 2O (M=Mn, Co, Ni, Zn, and X=S, Se) with matrix-isolated X′O 42− and M′ 2+ guest ions are presented and discussed in the region of the OD stretching modes. The OD frequencies indicate that the compounds under investigation form comparatively strong hydrogen bonds. The frequency shifts of the uncoupled OD stretching modes of the HDO molecules within the isostructural series and those influenced by the guest ions, and the strength of the hydrogen bonds formed, are discussed in terms of the respective O wO distances, which hint at stronger hydrogen bonds for the sulfate series than for the selenate one by mistake, the larger hydrogen bond acceptor capability of SeO 42− ions compared to SO 42− ones, the different metal–water interactions and repulsion potentials of the lattice, and the reorientation of the water molecules caused by the guest ions. The shifts of the OD stretches of the ODOSe′O 3 bonds (Se′O 42− matrix isolated) to the lower wavenumbers as compared to the parent selenates are caused by the reorientation of the hydrate water molecules and strengthening the hydrogen bond to the stronger acceptor and vice versa. When smaller metal ions having smaller M–OH 2 bond lengths and, hence, stronger synergetic effect replace larger ones, the OD stretches are shifted to lower wavenumbers as compared to those due to the host M–O wO bonds and vice versa. 相似文献
8.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
9.
The resistance of a novel silica-based N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption material (TODGA/SiO 2-P) against nitric acid, temperature and γ-irradiation had been investigated. The adsorption property of the treated TODGA/SiO 2-P was evaluated by a 3 M HNO 3 solution containing 0.01 M Nd(III). It was found that both 3 and 0.01 M HNO 3 concentrations did not decrease the stability of TODGA/SiO 2-P at 25°C. The quantity of TODGA leaked from TODGA/SiO 2-P was equivalent to its solubility in the corresponding HNO 3 aqueous solution. The effect of 3 M HNO 3 on the leakage of TODGA at 80°C was significantly higher than that in 0.01 M HNO 3 as well as in all cases at 25°C. The amount of Nd(III) adsorbed towards the treated TODGA/SiO 2-P was determined in the range of 0.143–0.148 mmol/g for the HNO 3 concentration effect and 0.142–0.0506 mmol/g for the temperature effect. γ-Irradiation showed a more noticeable destruction effect on TODGA/SiO 2-P. The content of TODGA leaked increased with an increase in the γ-irradiation dose (ID) from 1.06 to 3.72 MGy in terms of the linear equation [TODGA]=794.5ID+84.0. The amount of Nd(III) adsorbed onto the irradiated TODGA/SiO 2-P decreased rapidly from 0.134 to 0.0438 mmol/g, which was lower than 0.153 mmol/g, the adsorption of fresh TODGA/SiO 2-P for Nd(III), according to the equation QNd(III)=−0.0301ID+0.160, showing that a large quantity of TODGA leaked from TODGA/SiO 2-P. The adsorbed amount of Nd(III) decreased obviously in this order: the HNO 3 concentration effect, temperature effect and γ-irradiation. 相似文献
10.
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C 5Me 4CH 2PMe 2)], where M=Li + (1), Na + (2), or K + (3), and [Li(C 5H 4CR′ 2PMe 2)], where R′ 2=Me 2 (4), or (CH 2) 5 (5), [HC 5Me 4CH 2PMe 2H]X, where X −=Cl − (6) or PF 6− (7) and [HC 5Me 4CH 2PMe 2] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C 5R 4CR′ 2PMe 2) 2], where R=Me, R′=H (9); R=H and R′ 2=Me 2 (10), or (CH 2) 5 (11), [Fe(η-C 5H 4CMe 2PMe 3) 2]I 2 (12), [Fe{η-C 5Me 4CH 2P(O)Me 2} 2] (13), [Zr(η-C 5R 4CR′ 2PMe 2) 2Cl 2], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C 5H 4CMe 2PMe 2) 2]Cl 2] (16), [Zr(η-C 5H 4CMe 2PMe 2) 2Me 2] (17), {[Zr(η-C 5Me 4CH 2PMe 2) 2]Cl}{(C 6F 5) 3BClB(C 6F 5) 3} (18), [Zr{(η-C 5Me 4CH 2PMe 2) 2Cl 2}PtI 2] (19), [Mn(η-C 5Me 4CH 2PMe 2) 2] (20), [Mn{(η-C 5Me 4CH 2PMe 2B(C 6F 5) 3} 2] (21), [Pb(η-C 5H 4CMe 2PMe 2) 2] (23), [Sn(η-C 5H 4CMe 2PMe 2) 2] (24), [Pb{η-C 5H 4CMe 2PMe 2B(C 6F 5) 3} 2] (25), [Pb(η-C 5H 4CMe 2PMe 2) 2PtI 2] (26), [Rh(η-C 5Me 4CH 2PMe 2)(C 2H 4)] 29, [M(η,κ P-C 5Me 4CH 2PMe 2)I 2], where M=Rh (30), or Ir, (31). 相似文献
11.
The structures of 3,3′-dicarbometoxy-2,2′-bipyridine ( dcmbpy) complexes with copper(II) and silver(I) cations have been determined using single crystal X-ray-diffraction. The crystals of Cu( dcmbpy)Cl 2 are monoclinic, C2/ c, a = 16.966(3), b = 18.373(3), c = 13.154(2) Å, β = 126.543(3)°. The crystals of Ag( dcmbpy)NO 3 · H 2O are also monoclinic, C2/ c, a = 16.7547(13), b = 11.0922(9), c = 18.7789(18) Å, β = 100.228(7)°. The results have been compared with the literature data on the complexes of dcmbpy and its precursors: 2,2′-bipyridine ( bpy) and 3,3′-dicarboxy-2,2′-bipyridine ( dcbpy). Two types of complexes of 3,3′-carboxy derivatives of bpy are distinguished: (1) with metal atom bonded to two N atoms of the same molecule and (2) with metal atom bonded to two N atoms of two different molecules. The Cu( dcmbpy)Cl 2 complex belongs to the first type, whereas Ag( dcmbpy)NO 3 · H 2O belongs to the second type. 相似文献
12.
Using velocity map ion imaging technique, the photodissociation of n-C 4H 9Br in the wavelength range 231–267 nm was studied. The results and our ab initio calculations indicated that the absorption of n-C 4H 9Br in the investigated region originated from the excitations to the lowest three repulsive states, as assigned as 1A″, 2A′ and 3A′ in C s symmetry. Dissociations occurred on the PES surfaces of the three states, terminating in C 4H 9+Br ( 2P 3/2) or C 4H 9 + Br * ( 2P 1/2) as two channels, and being impacted by an avoided crossing between the PES surfaces of the 2A′ and 3A′ states. The transition dipole to the 1A″ state was perpendicular to the symmetry plane, so perpendicular to the C–Br bond. The transitions to the 3A′ state was polarized parallel to the symmetry plane, and also parallel to the C–Br bond. While the transition dipole to the 2A′ state was in the symmetry plane, but formed an angle of about 53.1° with the C–Br bond. We have also determined the avoided crossing probabilities, which affected the relative fractions of the individual pathways, for the photolysis of n-C 4H 9Br near 234 nm and 267 nm. 相似文献
13.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
14.
A series of Cu(II) complexes of disubstituted 2,2′-bipyridine bearing ammonium groups [Cu(L 1−4) 2Br] 5+ (1–4, L 1 = [5,5′-(Me 2NHCH 2) 2-bpy] 2+, L 2 = [5,5′-(Me 3NCH 2) 2-bpy] 2+, L 3 = [4,4′-(Me 2NHCH 2) 2-bpy] 2+, L 4 = [4,4′-(Me 3NCH 2) 2-bpy] 2+ and bpy = 2,2′-bipyridyl) were synthesized, of which complexes 1 and 4 were structurally characterized. Both coordination configurations of Cu(II) ions can be described as distorted trigonal bipyramid. The interaction between all complexes and CT-DNA was evaluated by thermal-denaturation experiments and CD spectroscopy. Results show that the complexes interact with CT-DNA via outside electrostatic interactions and their binding ability follows the order: 1 > 2 > 3 > 4. In the absence of any reducing agents, the cleavage of plasmid pBR322 DNA by these complexes was investigated and the hydrolysis kinetics of DNA was studied in Tris buffer (pH 7.5) at 37 °C. Obtained pseudo-Michaelis–Menten kinetic parameters: 15.0, 13.6, 2.01 and 1.69 h −1 for 1, 2, 3 and 4, respectively, indicate that complexes 1 and 2 exhibit very high DNA cleavage activities. According to their crystal data, the high nuclease activity may be attributed to the strong interaction of the metal moiety and two ammonium groups with phosphate groups of DNA. 相似文献
15.
The 2,2′-dimethyl-4,4′-bithiazole ligand (1), (dm4bt), and its Zn and Hg complexes have been prepared. A conformational property calculation at the DFT level for the ligand shows the anti conformation is energetically more stable by about 22.83 kJ/mol and the rotational barrier is about 32.01 kJ/mol for the anti → syn conversion, a phenomena happening during complex formation. The complexes [Zn(dm4bt)Cl 2] (2) and [Hg(dm4bt)Cl 2] (3) have spectral properties typical for d 10 metal diimine systems. The structures of the ligand and the two complexes have been determined by the single crystal diffraction method. The X-ray structure determinations show that both complexes are four coordinated by two chloride atoms and one bidentate dm4bt. In the Hg complex one of the two chlorides is set at a semi-bridging position. 相似文献
16.
The potential of Fe(CO) 4(η 1-dppf) (dppf = 1,1′-bis(diphenylphosphino)ferrocene) as a precursor for heterometallic species is fully expanded in the synthesis of (OC) 4Fe(μ-dppf)Cr(CO) 5, (OC) 4Fe(μ-dppf)W(CO) 5, and (OC) 4Fe(μ-dppf)Mn 2(CO) 9, all of which have been characterized by IR, NMR ( 1H and 31P) and elemental analyses. The low energy requirement of TMNO (Me 3NO · 2H 2O)decarbonylation allows the formation of monosubstituted Mn 2(CO) 10 as the major product. This aspect is further substantiated by the isolation of Mn 4(CO) 18(μ-dppf) in which the single bridging of a diphosphine group between two Mn 2(CO) 9 moieties is unprecedented. 相似文献
17.
Toluene solutions of M 2(NMe 2) 6 (M = Mo, W) react with mesitylene selenol (Ar′SeH) to give M 2(SeAr′) 6 complexes. MO 2(OR) 6 (R = tBu, CH 2tBu) react with excess> 6 fold) Ar′SeH to give Mo 2 (SeAr′) 6, whilst W 2(OR) 6(py) 2 (R = iPr, CH 2tBu) react with excess (> 6 fold) Ar′SeH to give W 2(OR) 2(SeAr′) 4. Reaction of MO 2(OPr i) 6 with Ar′SeH produces Mo 2(OPr i) 2 (SeAr′) 4 which crystallizes in two different space groups. These areneselenato complexes are air-stable and insoluble in common organic solvents. X-ray crystallographic studies revealed that the Mo 2(SeAr′) 6 and W 2(SeAr′) 6 compounds are isostructural in the solid state and adopt ethane-like staggered configurations with the following important structural parameters, M---M (W---W/Mo---Mo) 2.3000(11)/2.2175(13) Å, M---Se 2.430 (av.)/2.440 (av.) Å, M---M---SE 97.0° (av.)°. In the solid state W 2(O iPr) 2(SeAr′) 4 adopts the anti-configuration with crystallographically imposed Ci symmetry and W---W 2.3077(7) Å, W---Se 2.435 (av.) Å, W---O 1.858(6) Å; W---W---SE 100.27(3)°, 93.8(3)° and W---W---O 108.41(17)°. Mo 2(OPr i) 2(SeAr′) 4 crystallizes in both P
and A2/ a space groups in which the molecules are isostructural with each other and the tungsten analogue. Important bond lengths and angles are Mo---Mo 2.180(24) Å, Mo---Se 2.432(av.) Å, Mo---O 1.872(9) Å, Mo---Mo---Se 99.39(9)°, 94.71(8)°, Mo---Mo---O 107.55(28)°. 相似文献
18.
Reactions of FcCCH (a), HCCCCFc (b) and FcCCCCFc (c) with Ru 3(CO) 10(NCMe) 2 (all) and Ru 3(μ-dppm)(CO) 10 (b and c only) are described. Among the products, the complexes Ru 3(μ 3-RC 2R′)(μ-CO)(CO) 9 (R=H, R′=Fc 1, CCFc 2; R=R′=Fc 5), Ru 3(μ-H)(μ 3-C 2CCFc)(μ-dppm)(CO) 7 3, Ru 3(μ 3-FcC 2CCFc)(μ-dppm)(μ-CO)(CO) 7 6 and Ru 3{μ 3-C 4Fc 2(CCFc) 2}(μ-dppm)(μ-CO)(CO) 5 7 were characterised, including single-crystal structure determinations for 1, 3, 5 and 7; that of 7 did not differ significantly from an earlier study of a mixed CH 2Cl 2–C 6H 6 solvate. 相似文献
19.
The reactions of RNHSi(Me) 2Cl (1, R= t-Bu; 2, R=2,6-(Me 2CH) 2C 6H 3) with the carborane ligands, nido-1-Na(C 4H 8O)-2,3-(SiMe 3) 2-2,3-C 2B 4H 5 (3) and Li[ closo-1-R′-1,2-C 2B 10H 10] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me) 2N(H)R]-2,3-(SiMe 3) 2-2,3-C 2B 4H 5, (5, R= t-Bu) and closo-1-R′-2-[Si(Me) 2N(H)R]-1,2-C 2B 10H 10 (6, R= t-Bu, R′=Ph; 7, R=2,6-(Me 2CH) 2C 6H 3, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me) 2NH(2,6-(Me 2CH) 2C 6H 3)]-1,2-C 2B 10H 11 (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [ nido-3-{Si(Me) 2N(2,6-(Me 2CH) 2C 6H 3)}-1,3-C 2B 10H 11] 3− (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl 4 (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d 0-metallacarborane, closo-1-M[(Cl)(THF) n]-2-[1′-η 1σ-N(2,6-(Me 2CH) 2C 6H 3)(Me) 2Si]-2,4-η 6-C 2B 10H 11 (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, 1H-, 11B-, and 13C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2 1/ c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) Å 3, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections. 相似文献
20.
Pyrolysis of a solution of {Ru 3(CO) 11} 2(μ-bdpp) (bdpp = bis(diphenylphosphino)butadiyne) yielded the complex {Ru 3(μ-PPh 2)(CO) 9} 2(μ 6-C 4), which contains a μ 6-C 4 ligand symmetrically bridging two Ru 3(μ-PPh 2)(CO) 9 clusters. When the complex {Fe(CO) 4} 2(μ-bdpp) was heated in the presence of Fe 2(CO) 9 another example of a C 4 complex, {Fe 2(μ-PPh 2)(CO) 6} 2(μ-C 4), was obtained. Both complexes were characterised by X-ray structure determinations; the C 4 ligand behaves as a buta-1,3-diyne-1,4-diyl system. 相似文献
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