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1.
Zusammenfassung Die Absorptions- und Reflexionsspektren der Oktocyanokomplexe des Mo(IV) und W(IV) sowie die Absorptionsspektren der Oktocyanotomplexe des Mo(V) und W(V) werden mitgeteilt. Die Spektren werden unter Zugrundelegung der durch Raman- und IR-spektroskopische Untersuchungen geforderten D
4d-Symmetrie dieser Verbindungen interpretiert. Die beobachteten Banden niedriger Intensität (log <3) werden Übergängen in einem Termsystem zugeordnet, das für die Konfigurationen d
2 und d
1 und die Symmetrie D
4d berechnet worden ist. Banden hoher Intensität (log >3) werden auf Übergänge in antibindende Zustände zurückgeführt, an denen höhere p-Zustände des Zentralions sowie Ligandenzustände beteiligt sind. Die erhaltenen Werte des Feldparameters stimmen mit ligandenfeldtheoretischen Erwartungen überein.
Absorption and reflection spectra of the octacyanides ofMo(IV) andW(IV) and the absorption spectra of the octacyanides ofMo(V) andW(V) are presented. The spectra are interpreted in terms of theD
4d symmetry of the compounds supported by investigations of Raman and infrared spectra. Bands of low intensity (log<3) correspond to transitions between levels obtained in the case of the configurationsd
2 andd
1 respectively, in a field ofD
4d symmetry. Bands of high intensity (log>3) are attributed to transitions into antibonding levels in which p-orbitals of the central ion and ligand orbitals participate. The values of the field parameter obtained are in accord with ligand field theory.
Résumé Les spectres d'absorption et de réflexion des complexes octocyanurés duMo(IV) et duW(IV) ainsi que les spectres d'absorption des mêmes complexes deMo(V) et de W(V) sont présentés. Les spectres sont interprétés en supposant la symétrieD
4d des molécules indiquée par des analyses des spectres Raman et infrarouges. Les bandes de faible intensité (log<3) sont attribuées à des transitions dans un système de niveaux, calculé pour les configurationsd
2 etd
1, respectivement, en symétrieD
4d. Des bandes de forte intensité (log>3) sont attribuées à des transitions vers des niveaux antiliants auxquels participent des fonctions élevéesp de l'ion central et des fonctions des groupes liés. Les valeurs obtenues pour le paramètre de champ sont en accord avec les prévisions de la théorie. 相似文献
2.
Complexes [(4-MeC 6H 4) 4Sb] 2 + [Hg 2I 6] 2? ( I), [(4-MeC 6H 4) 4Sb] 2 + [HgI 4] 2? ( II), [(4-MeC 6H 4) 4Sb] 3 + [Sb 3I 12] 2? ( III), were synthesized by reactions of tetra- p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra- p-tolylantimony perrhenate [(4-MeC 6H 4) 4Sb] +[ReO 4] ? ( IV) was prepared from tetra- p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb 3I 12] 2? anions of complex III have an octahedral environment. Each terminal SbI 3 fragment (Sb-I t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I br, 3.0153(6)–3.0316(6) Å; Sb(3)-I br, 2.9926(6)–3.0074(6) Å). 相似文献
4.
Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions
[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate] 2−, [Q] 2[Sn(C 3S 5) 3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate] 2−, [Q] 2[Sn(C 3S 4O) 3], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate] 2− [Q] 2[Sn(C 3S 3Se 2) 3], complexes, have been synthesised and characterised. Crystal structure determinations of [Q] 2[Sn(C 3S 5) 3] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe 4, NEt 4, and PPh 4) and [NEt 4] 2[Sn(C 3S 4O) 3] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe 4, in chains for the somewhat larger cation, NEt 4 and is absent for the still larger, PPh 4 cation. 相似文献
5.
Russian Journal of Coordination Chemistry - The formation of complex salt [Ag(PPh3)4][2-B10H9NH3 ? 2DMF] (I) by the reaction of the salts of the [2-B10H9NH3]– anion with [Ag(PPh3)4]NO3... 相似文献
6.
The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph 3AmP] 2 + [Sb 2I 8 · 2DMSO] 2?, [Ph 3PrP] 2 + [Sb 2I 8 · C 4H 8O 2] 2?, and [(HOCH 2CH 2) 3NH] 4 + [Sb 4I 16] 4?, the structure of which was established by X-ray diffraction analysis. The cations of all complexes have slightly distorted tetrahedral structure, and the antimony atoms in the anions are hexacoordinated. The crystals of the complexes have intra- and intermolecular contacts, which form the structure. 相似文献
7.
The complex ion [Fe(CN) 6SO 3] 4− has been prepared in aqueous solution and as the zinc salt in the solid state. The electronic and IR spectra of the complex ion ( I) have been recorded. MO calculations have been performed to understand the electronic structure of complex I. The electronic spectra of I and hexacyanoferrate(II) [HCF(II)] have been calculated and compared with the experimental results for I, HCF(II) and HCF(III). The experimental and theoretical results suggest that the oxidation state of Fe in I is + 3 and not +2 and the SO 3 moiety is bonded to one of the nitrogen atoms of the cyano group. 相似文献
8.
Complexes with antimony-containing anions, [Ph 3MeP] + 2 [SbI 5] 2? ( I), [Ph 3MeP] + 2 [Sb 3I 12] 3? ( II), [Ph 3MeP] + 3 [Sb 3I 12] 3? · Me 2C=O ( III), and [Ph 3MeP] + 3 [Sb 2I 9] 3? ( IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI 3 groups is bound to the central Sb atom through two μ 2- and one μ 3 iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms. 相似文献
9.
Compounds that form in the CoSiF 6· 6H 2O–NioxH 2–A–water–alcohol system, where A is thiourea (Thio) or triphenylphosphine (PPh 3) and NioxH 2is 1,2-cyclohexanedione dioxime, were synthesized and characterized by X-ray diffraction analysis. Crystal structures of the [Co(NioxH) 2(PPh 3) 2]SiF 5and [Co(NioxH) 2(Thio) 2] 2SiF 6· 3H 2O complexes were established. In octahedral Co(III) complexes, two radicals of 1,2-cyclohexanedione dioxime are bound by a hydrogen bond and are located in the equatorial plane. The intramolecular (– and H bonds) and intermolecular (C–H···F and H bonds) interactions in the crystal are discussed. 相似文献
10.
The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph 4Sb] 2 + [Hg 2I 6] 2?·Ph 2Hg ( I). The [Ph 4Sb] 2 + [Hg 2I 6] 2? ( II) and [Ph 4Sb] 2 + [Cd 2I 6] 2? ( III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph 4Sb] 2 + [Hg 4I 10] 2? complex ( IV) is prepared from tetraphenylantimony 2,4-dimethylbenzenesulfonate and mercury iodide. According to the X-ray diffraction data, the Sb atom in the [Ph 4Sb] + cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg 2I 2 of the [Hg 2I 6] 2? anion, the Hg-I br bond lengths are 2.825 and 3.075 Å, and the terminal iodine atoms are more strongly bonded to the mercury atoms (Hg-I term 2.691 and 2.700 Å). The [Cd 2I 6] 2? anion in complex III has a similar structure (the Cd-I bridg and Cd-I term distances are 2.865, 2.872 and 2.723, 2.748 Å, respectively). The anions in complex IV are joined by I…Hg (3.651 Å) and I…I (4.058 Å) interactions into an infinite dimeric network. 相似文献
11.
A complete NMR study involving both 1D and 2D 13C-{ 103Rh} and 31P-{ 103Rh} HMQC measurements, on [Rh 6C(CO) 14(PPh 3)] 2- are reported and discussed, together with the multiple Rh quantum effects found for resonances associated with edge- and face-bridging CO's. As found in [Rh 6C(CO) 15] 2-, the carbonyl ligands in [Rh 6C(CO) 14(PPh 3)] 2- undergo CO-intermolecular exchange with 13CO at different rates; for the edge-bridging CO's, the lower the value of 1J(Rh–CO), the faster the rate of intermolecular exchange with 13CO. 相似文献
12.
Synthesizing solids in molten fluxes enables the rapid diffusion of soluble species at temperatures lower than in solid-state reactions, leading to crystal formation of kinetically stable compounds. In this study, we demonstrate the effectiveness of mixed hydroxide and halide fluxes in synthesizing complex Sr/Ag/Se in mixed LiOH/LiCl. We have accessed a series of two-dimensional Sr(Ag 1−xLi x) 2Se 2 layered phases. With increased LiOH/LiCl ratio or reaction temperature, Li partially substituted Ag to form solid solutions of Sr(Ag 1−xLi x) 2Se 2 with x up to 0.45. In addition, a new type of intergrowth compound [Sr 3Se 2][(Ag 1−xLi x) 2Se 2] was synthesized upon further reaction of Sr(Ag 1−xLi x) 2Se 2 with SrSe. Both Sr(Ag 1−xLi x) 2Se 2 and [Sr 3Se 2][(Ag 1−xLi x) 2Se 2] exhibit a direct band gap, which increases with increasing Li substitution ( x). Therefore, the band gap of Sr(Ag 1−xLi x) 2Se 2 can be precisely tuned via fine-tuning x that is controlled by only the flux ratio and temperature. 相似文献
13.
X-ray structural studies of new thermolysis products from the reaction of Ru 3(CO) 12 in heptane in the presence of 1,3,5-trimethylbenzene (mesitylene) confirm that they are the decaruthenium carbido-cluster dianion [Ru 10C(CO) 24] 2− (I) and the hydrido decaruthenium carbido-cluster monoanion [HRu 10C(CO) 24] − (II). Both anions have the giant tetrahedron Ru 10 metal framework, and the monohydride provides the first example of a hydrido ligand in a tetrahedral Ru 4 cavity. 相似文献
14.
The electrophoretic behavior of twenty anions has been studied on silica gel-G, titanium (IV) tungstate and silica gel-G- titanium (IV) tungstate admixture layers using 0.1 M solutions of oxalic acid, citric acid, tartaric acid, succinic acid and acetic acid as background electrolyte. The mechanism of migration is explained in terms of adsorption and the solubility of various sodium or potassium salts of the anions in water. Titanium (IV) tungstate behaves only as an adsorbent and not as an ion exchanger. Being a cation exchanger, there is no exchange phenomenon occurring with anions. The migration of halides increase linearly with an increase in the bare ion radii of these ions. Differential migration of the anions on silica gel-G layers led to binary, ternary and quaternary separations of similar anions such as F− – Cl− – Br− – I−, I− – IO3− – IO4−, BrO3− – IO3− and Fe(CN)63− – Fe(CN)64−. The two cyanoferrate ions are separated from industrial waste water and from fixer and bleach solutions. The migration of anions has also been found to be in accordance with their lyotropic numbers. 相似文献
15.
The [NpO 2(DPPMO 2) 2Cl][NpO 2Cl 4] complex (where DPPMO 2 = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO 2} 2+, with two bidentate P=O donor ligands. Coordinating anion Cl ? fills the fifth equatorial coordination site yielding a complex of general formula [NpO 2(DPPMO 2) 2X] 2[Y] ( 1) (where X = Cl ? and Y = [NpO 2Cl 4] 2?. Reaction between our newly prepared neptunium starting material [NpO 2Cl 2(thf)] n and phosphinimine ligand produced crystals of [Ph 3PNH 2] 2[NpO 2Cl 4] ( 2). Compounds 1 and 2 have been structurally characterised. 相似文献
16.
The mononuclear complex (NMe 4) 3[Re( 2-CS 3) 4] has been prepared by adding CS 2 to ReS –
4 in a mixture of MeOH and NH 3. During the reaction, Re VII is reduced to Re V, the measured diamagnetism ( X = –3.04 × 10 –4cm 3mol –1) of the complex showing that the two added electrons are coupled. (NMe 4) 3[Re( 2-CS 3) 4] crystallizes in the space group Fddd, a = 11.985(4) Å, b = 23.001(11) Å, c = 47.463(19) Å, V = 13085(9) Å 3. The reaction of CS 2 results in the formation of trithiocarbonates bonded to the rhenium in a dodecahedral geometry. 相似文献
17.
The reactivity of the metalloligand [Pt 2(μ-S) 2(PPh 3) 4] with the boron-functionalized alkylating agents BrCH 2(C 6H 4)B(OR) 2 (R = H or C(CH 3) 2) was investigated by electrospray ionization mass spectrometry (ESI-MS) in real time using pressurized sample infusion (PSI). The macroscopic reaction of [Pt 2(μ-S) 2(PPh 3) 4] with one mole equivalent of alkylating agents BrCH 2(C 6H 4)B{OC(CH 3) 2} 2 and BrCH 2(C 6H 4)B(OH) 2 gave the dinuclear monocationic μ-sulfide thiolate complexes [Pt 2(μ-S){μ-SCH 2(C 6H 4)B{OC(CH 3) 2} 2}(PPh 3) 4] + and [Pt 2(μ-S){μ-S +CH 2(C 6H 4)B(OH)(O ?)}(PPh 3) 4]. The products were isolated as the [PF 6] ? salt and zwitterion, respectively, and fully characterized by ESI-MS, IR, 1H and 31P NMR spectroscopy, and single-crystal X-ray structure determinations. 相似文献
18.
The oxidation of the [Fe(CO) 4] 2– dianion with Ag + salts occurs through a particular inner-sphere mechanism, which involves an intermediate cascade of silver clusters stabilized by Fe(CO) 4 ligands. The last detectable Ag-Fe cluster of the sequence is the [Ag 13{ -Fe(CO) 4} 8] 3– trianion, which has been selectively obtained by using ca. 1.7 equivalents of Ag + per mole of [Fe(CO) 4] 2–. The [Ag 13{ -Fe(CO) 4} 8] 3–- trianion has been isolated in a crystalline state with several quaternary cations, and has been characterized by X-ray diffraction studies of its bis(triphenylphosphine)iminium salt. [N(PPh 3) 2] 3 [Ag 13{
3-Fe(CO) 4} 8]·2(CH 3) 2CO, monoclinic, space group P2 1 (No.4), a = 16.284(2) Å, b =18.767(5) Å, c = 25.905(4) Å, = 90.46(1)°, V = 7916(3) Å 3, Z = 2, R = 0.0324. The molecular structure of the anion consists of a centered cuboctahedron of silver atoms with the triangular faces capped by Fe(CO) 4 units. Chemical reduction of ( Ag 13{
3-Fe(CO) 4} 8] 3– affords the corresponding [Ag 13{
3-Fe(CO) 4) 8] 4–, which in turn gives [Ag 13{
3-Fe(CO) 4) 8] 5– and [Ag 6{
3-Fe(CO) 4} 4] – upon further reduction. Electrochemical investigations confirm the reversibility of the [Ag 13{
3-Fe(CO) 4} 8] 3–/4– redox change. Furthermore, in spite of some electrode poisoning effects, evidence of the existence of the [Ag 13{
3-Fe(CO) 4} 8] 5– pentaanion was obtained. The yet structurally uncharacterized [Ag 6{
3-Fe(CO) 4) 4] 2– dianion is quantitatively obtained by reaction of [Fe(CO) 4] 2– with ca. 1.5 equivalents of Ag + or by addition of one equivalent of Ag + to solutions of the [Ag 5{Fe(CO) 4} 4] 3– trianion. All attempts to isolate its quaternary salts as crystalline materials failed owing to formation of amorphous insoluble precipitates. The above series of
3-Fe(CO) 4 octa-capped cuboctahedral Ag 13 clusters can be envisioned as the Ag + . Ag and Ag – cryptates of the [Ag 12{} 3-Fe(CO) 4} 8] 4– cryptand. respectively.Dedicated to Prof L. F. Dahl on his 65th birthday. 相似文献
20.
The structural characterization of the osmahexaborane 2-carbonyl-2,2-bis(triphenylphosphine)- nido-2-osmahexaborane(9), [Os(B 5H 9)(C 18H 15P) 2(CO)], (I), a metallaborane analogue of B 6H 10, confirms the structure proposed from NMR spectroscopy. The structure of the osmadecaborane 6-carbonyl-6,6-bis(triphenylphosphine)- nido-6-osmadecaborane(13), [Os(B 9H 13)(C 18H 15P) 2(CO)], (IV), is similarly confirmed. The short basal B—B distance of 1.652 (8) Å in (I), not bridged by an H atom, mirrors that in the parent hexaborane(10) [1.626 (4) Å]. 相似文献
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