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1.
Summary The preparation and characterization of salts of the [ReO2(CN)4]3–, [ReO(OH)(CN)4]2–, [ReO(H2O)(CN)4]–, [Re2O3(CN)8]4– and [ReO(NCS)(CN)4]2– species are described. The nature of the protonation reactions of [ReO2(CN)4]3– was established by the successful isolation of these salts.  相似文献   

2.
Zusammenfassung Es wurden 39 neue Komplexsalze durch doppelte Umsetzung aus wäßrig-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)4(o-Toluidin)2]–, [Cr(NCS)4(m-Toluidin)2]– und [Cr(NCS)4(p-Toluidin)2]– und Hexammin-, Monoacido-pentammin-und Diacido-tetrammin-kobalt(III)-komplexsalze erhalten.Es wurden in einigen Fällen Abweichungen in physikochemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR F-Werte, bei den stellungsisomeren Salzen vom Typus: Kation·[Cr(NCS)4(Toluidin)2] und auch bei den Koordinationsisomerpaaren: [Co(DH)2(o-Toluidin)2][Cr(NCS)4(p-Toluidin)2] und [Co(DH)2(p-Toluidin)2] [Cr(NCS)4(o-Toluidin)2], usw. beobachtet.
Cobalt(III) ammine derivatives of some reineckate analogues with toluidines
39 new complex salts were prepared by double conversion of the reineckate analogues [Cr(SCN)4(o-toluidine)2]–, [Cr(SCN)4(m-toluidine)2]–, and [Cr(SCN)4(p-toluidine)2]– with the hexammine, monoacido-pentammine and diacido-tetrammine complexes of Co(III). In some of the position and coordination isomers deviations from the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR f-values were observed.
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3.
Syntheses and Structures of (Et4N)2[Re(CO)3(NCS)3] and (Et4N)[Re(CO)2Br4] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et4N)2[Re(CO)3Br3]. Using nonoxidizing reagents the facial ReI(CO)3 unit remains and only the bromo ligands are exchanged. Following this procedure, (Et4N)2[Re(CO)3(NCS)3] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P21/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS? ligands are coordinated via nitrogen. The reaction of [Re(CO)3Br3]2? with Br2 yields the rhenium(III) anion [Re(CO)2Br4]?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc21, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.  相似文献   

4.
This paper reports on EXAFS and XANES studies of structural changes in complex compounds (H3O)2Co3[Re6Se8(CN)6]214.5H2O, Cs2Co[Re6S8(CN)6]2H2O, and Co(DMF)6[Mo6Br8(NCS)6] containing the octahedral cluster anions of rhenium [Re6X8(CN)6]4– (X = S, Se) or molybdenum [Mo6Br8(NCS)6]2–, induced by vacuum annealing at temperatures of up to 250°C. According to EXAFS and XANES data, the complex cluster anions do not undergo any pronounced changes during annealing. The parameters of the local environment of the cobalt cations have been determined. Structural models of the environment of the cations in various compounds after desolvation have been constructed. For Co(DMF)6[Mo6Br8(NCS)6], vacuum annealing at 250°C leads to a complete removal of DMF and formation of a new compound, Co[Mo6Br8(NCS)6], in which the cobalt atoms are coordinated by four sulfur atoms of the SCN groups.  相似文献   

5.
The pyrolyses of [NEt4][H2Re(CO)4] in boiling n-heptane, n-octane and n-nonane are described. Mixtures of polynuclear carbonyl- and hydridocarbonylrhenium species are obtained, the principal products being [Re4(CO)16]2?, [H2Re3(CO)12], [H3Re3(CO)10]2?, [H3Re3O(CO)9]2? and [H6Re4(CO)12]2?. A red-orange crystalline species was isolated from the reaction in n-heptane and shown by X-ray diffraction to be [Net4]2[HRe3(CO)12]. It gives orthorhombic crystals, space group Pbca, with cell constants a 16.07(1), b 23.39(2), c 19.49(1) Å. The structure was solved by Patterson and Fourier methods and refined by least-squares up to a final R value of 0.061, for 1303 independent counter data. The anion [HRe3(CO)12]2? contains an isosceles metal atom triangle, with two short edges of 3.014(3) and 3.018(3) Å and a long hydrogen-bridged edge of 3.125(3) Å.  相似文献   

6.
The thermally stable solids Re2(CO)8[μ-InRe(CO)5]2 and Re4(CO)12[μ3-InRe(CO)5]4 could be obtained by treatment of In with Re2(CO)10 in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re2(CO)8[μ-InRe(CO)5]2, Re4(CO)12[μ3_InRe(CO)5]4 shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re4(CO)12-[μ3-InRe(CO)5]4 dissolves monomerically in acetone, where as Re2(CO)8[μ-InRe(CO)5]2 dissociates yielding Re(CO)5? anions. Single-crystal X-ray analyses of Re4(CO)12[μ3-InRe(CO)5]4 establish the metal skeleton. The central molecular fragment Re4(CO)12 contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ3-InRe(CO)5 group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re4 tetrahedron and the metal skeleton was realized for the first time. By treating Re4(CO)12[μ3-InRe(CO)5]4 with Br2 the existence of Re(CO)5 ligands could be proved by isolating BrRe(CO)5.  相似文献   

7.
Zusammenfassung Es wurden 34 neue Komplexsalze durch doppelte Umsetzung aus wäßr.-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)4(m-xylidin)2]–, [Cr(NCS)4(p-xyl)2]– und Hexammin-, Monoacido-pentammin- und Diacido-tetramminkobalt(III)-komplexsalze erhalten. Es wurden in einigen Fällen Unterschiede in physiko-chemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR f-Werte, bei den stellungsisomeren Salzen vom Typus: Kation · [Cr(NCS)4(xyl)2] und auch bei den Koordinationsisomerpaaren: [Co(DH)2(m-xyl)2] [Cr(NCS)4(p-xyl)2] und [Co(DH)2(p-xyl)2] [Cr(NCS)4(m-xyl)2] usw. beobachtet.
Cobalt(III)ammine derivatives of some reineckate analogues with xylidines
34 new complex salts were prepared by double conversion of the reineckate analogues [Cr(NCS)4(m-xylidine)2]–, [Cr(NCS)4(p-xyl)2]–, with the hexammine-, monoacido-pentammine- and diacidotetrammine-complexes of Co(III). In some of the position and coordination isomeres differences of the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR f-values were observed.
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8.
The cationic dibenzocyclamnickel(II) complex, [Ni(Me4Bzo2[14]aneN4)]2+, was obtained in good yield by Fe/HCl reduction of the corresponding tetraazaannulene complex [Ni(Me4taa)], (1) {Me4Bzo2[14]aneN4 = 5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraazacyclotetradecane; Me4taa = 5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraazaannulene(2-)}. The orange–red product was isolated as the chloride (2) and perchlorate (3) salts. Analogous reduction with Zn/HCl yielded a diprotonated silky-white product [Ni(Me4Bzo2[14]aneN4-H2)][ZnCl4]2, (4). In the dry state, complex (4) is stable only under an HCl atmosphere and readily dissociates to give a solution of (2) when dissolved in polar solvents. Complexes (2) and (3), upon treatment with an excess of aqueous NaCN, undergo facile demetallation yielding the metal free macrocycle Me4Bzo2[14]aneN4, (5). These compounds were characterized using a combination of i.r., u.v.–vis., 1H-n.m.r., mass spectroscopy and voltammetry techniques. Unlike the parent tetraazaannulene complex (1), the reduced macrocycle complex, [Ni(Me4Bzo2[14]aneN4)]2+ exhibits mild catalytic activity towards electro-reduction of CO2 in MeCN solution.  相似文献   

9.
Mono-and dinuclear ReIV and ReV complexes with 3,5-dimethylpyrazole (Me2pzH) were synthesized. The cis-[Re2O3Cl4(3,5-Me2pzH)4] complex (cis-1) was prepared by the reaction of NH4ReO4 with K[HB(Me2pz)3] in concentrated HCl or by refluxing of [ReCl3(MeCN)(PPh3)2] with Me2pzH in air. The bromide complex trans-[Re2O3Br4(3,5-Me2pzH)4] (trans-2) was synthesized by passing dry HBr through a solution of [Re2O3Br2(μ-3,5-Me2pz)2(3,5-Me2pzH)2] (4) in chloroform. The pyrazolate-bridged complex [Re2O3Cl2(μ-3,5-Me2pz)2(3,5-Me2pzH)2] (3) was prepared from (Et4N)2[ReOCl5] or Cs2[ReOCl5] and Me2pzH. The corresponding bromide and iodide complexes [Re2O3X2(3,5-Me2pz)2(3,5-Me2pzH)2] · C6H6 (X = Br (4) or I (5)) were synthesized by the reactions of (NH4)2[ReBr6] or K2[ReI6], respectively, with Me2pzH. The [ReO(OMe)(3,5-Me2pzH)4]Br2 · · 3,5-Me2pzH · 4H2O complex (6) was obtained as a by-product in the synthesis of complex 4. The reaction of [ReNCl2(PPh3)2] with Me2pzH was accompanied by hydrolytic denitration giving rise to the mixed-ligand complex [Re2O3Cl2(μ-3,5-Me2pz)2(3,5-Me2pzH)(PPh3)] (7). The reaction of (NH4)2[ReBr6] with a Me2pzH melt gave the trans-[ReBr4(3,5-Me2pzH)2] · · Me2CO complex (8). The structures of complexes 2 and 4–8 were established by X-ray diffraction. All compounds were characterized by elemental analysis, electronic absorption spectroscopy, 1H NMR and IR spectroscopy, mass spectrometry, and cyclic voltammetry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 52–59, January, 2006.  相似文献   

10.
The octahedral cluster anion [Re6Se6Br8]2– was prepared by high-temperature synthesis from elementary substances in the presence of KBr. This cluster anion was isolated and structurally characterized by single-crystal X-ray diffraction analysis as the (PPh4)2[Re6Se6Br8] complex (1). Refluxing of polymeric rhenium selenide bromide Re6Se6Br6 in DMF in the presence of Bu4NBr led to the cleavage of the Re—Br—Re bridges to form the complex (Bu4N)2[Re6Se6Br8]. Comparative analysis of the interatomic distances in the octahedral rhenium(iii) selenide bromide clusters was carried out.  相似文献   

11.
The cluster anions [Re6X8(CN)6]34– (X = S, Se, or Te) containing 23 cluster valence electrons in the Re6 octahedron were synthesized and isolated as salts with organic cations. The crystal structures of the (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O, and (Et4N)2(H)[Re6Te8(CN)6]·2H2O clusters were solved by X-ray diffraction analysis. Removal of one electron has virtually no effect on the geometry and interatomic distances in the cluster anion but leads to a substantial change in the electronic spectrum and to an increase in stretching vibration frequencies CN compared to those of the [Re6X8(CN)6]4– anions.  相似文献   

12.
Zusammenfassung Auf Grund spektrophotometrischer, potentiometrischer und konduktometrischer Befunde entstehen aus [Co(HMPT)4]2+ in Hexamethylphosphorsäuretriamid (HMPT) bei Zusatz von Pseudohalogenidionen folgende Koordinationsformen: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3]–, [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3]–, [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3]–, [Co(HMPT)(CN)5]3–.
Hexamethyl phosphoric triamide as a ligand, III: Reactions of [Co(HMPT)4]2+ with rhodanide, cyanide, and azide ions, resp
Spectrophotometric, potentiometric and conductometric results indicate that addition of pseudohalide ions to [Co(HMPT)4]2+ in hexamethylphosphoramide (HMPT) leads to the following coordination forms: [Co(HMPT)3N3]+, [Co(HMPT)2(N3)2], [Co(HMPT)(N3)3]–, [Co(N3)4]2–, [Co(HMPT)3NCS]+, [Co(HMPT)2(NCS)2], [Co(HMPT)(NCS)3]–, [Co(NCS)4]2–, [Co(HMPT)2(CN)2], [Co(HMPT)(CN)3]–, [Co(HMPT)(CN)5]3–.

Mit 7 Abbildungen

2. Mitt.:V. Gutmann undA. Weisz, Mh. Chem.100, 2104 (1969).  相似文献   

13.
The Reaction of Dichlorophenylborane with Nitrido Complexes of Rhenium BCl2Ph reacts with terminal nitrido ligands of rhenium complexes under formation of a nitrogen bridge between the transition metal and boron. Structural studies on [Re(NBCl2Ph)Cl2(Ph3P)2], [Re(NBCl2Ph)Cl2(Me2PhP)3], [Re(NBCl2Ph)Cl(Me2PhP)2(Et2dtc)] and [Re(NBCl2Ph)(Me2PhP)(Et2dtc)2] (Et2dtc– = N,N′‐diethyldithiocarbamate) demonstrate that the rhenium‐nitrogen bond is only slightly lengthened upon the formation of the nitrido bridge whereas a significant decrease of the structural trans influence of the nitrido ligand is observed. [Re(NBCl2Ph)Cl4(Y)]– (Y = Cl or solvent) complexes are formed during the reaction of [ReNCl4]– with BCl2Ph. The rhenium(VI) compounds (d1configuration) can easily be detected by EPR spectroscopy. The formation of {Re(NBCl2Ph)} complexes with mixed Cl–/Br– (or NCS–) coordination spheres is evident when the reactions start from [ReNBr4]– or [ReN(NCS)5]2– which can be derived from the EPR spectra of the reaction mixtures.  相似文献   

14.
Reaction of polymeric compound Cs4[Re6S8(CN)4S2/2] with aqueous solution of KOH led to formation of trans-[Re6S8(CN)4(OH)2]4− anion which was crystallized in ordered Cs1.68K2.32[Re6S8(CN)4(OH)2] · 2H2O (1a) and disordered Cs1.83K2.17[Re6S8(CN)4(OH)2] · 2H2O (1b) modifications. The presence of two types of apical ligands, inert cyanides and labile hydroxides, opened a way to other trans-[Re6S8(CN)4L2] n− rhenium cluster complexes: trans-[Re6S8(CN)4Cl2]4−, trans-[Re6S8(CN)4(H2O)Br]3−, and trans-[Re6S8(CN)4Br2]4−, crystallized as Cs1.84K1.16(H)[Re6S8(CN)4Cl2] (2), Cs1.68K1.32[Re6S8(CN)4(H2O)Br] (3), (Me4N)3(H5O2)[Re6S8(CN)4Br2] (4), and CsK{Cu(H2O)2[Re6S8(CN)4Cl2]} · 4H2O (5) salts.  相似文献   

15.
Strain measurement and quasiequilibrium thermogravimetry were used to study the dissociation processes of two clathrates, [Ni(MePy)4(NCS)2]·(MePy) and [Cu(MePy)4(NCS)2]·2/3(MePy), accompanied by the liberation of MePy into the gaseous phase. In the Ni clathrate dissociation process in the temperature range 298–368 K the liberated MePy was redistributed between the solid clathrate and gaseous phases; the MePy vapour pressure over the clathrate is a function of temperature and the guest contenty, which agrees with the presence in the MePy-[Ni(MePy)4(NCS)2] system of a wide range of -clathrate solutions, [Ni(MePy)4(NCS)2]·y(MePy). The same methods used to study the Cu clathrate dissociation resulted in conclusions different from those obtained for the dissociation process of the above clathrate: the process is described by the equation [Cu(MePy)4(NCS)2]·2/3(MePy)solid =[Cu(MePy)2(NCS)2]solid+22/3(MePy)gas; the temperature dependence of the Mepy vapour pressure over the solid sample does not depend on its composition, which points to the absence from the system of solid solutions based on the clathrate. Standard changes of the enthalpy, entropy, and isobaric-isothermal reaction potential for the temperature range 292–325 K are equal to 178.6±1.7 kJ (mole of clathrate)–1, 463±5.6 J (mole of clathrate)–1 K–1, and 40.4±2.4 kJ (mole of clathrate)–1, respectively.  相似文献   

16.
Fusion of K2[Re(NO)Cl5] with KSCN produces the ion [Re(NO)(SCN)5]2? which has been isolated as free acid and K+, Na+, NMe4+, Pb2+, Hg2+, phen H+ and dipyH+ salts. A salt of composition Hg2[Re(NO)(SCN)7] has also been prepared. The species [Re(NO)Cl(SCN)4]2? has been obtained from the reaction of H2[Re(NO)(SCN)5] with HCl in aqueous medium and its NMe4+ salt has been isolated. Hydrated Re(NO)Cl3 reacts with KSCN in aqueous medium to produce the ion [Re(NO)Cl2(SCN)3]2? which has been isolated as its phenH+ and dipyH+ salts. The complexes have been characterized through elemental analyses, spectral (u.v., vis., i.r.) properties, magnetic and conductance data. The structures of all those compounds have been proposed.  相似文献   

17.
New octahedral anionic heterometal rhenium-osmium cluster complexes [Re5OsSe8(OH)6]3− and [Re4Os2Se8(OH)6]2− were synthesized starting from [Re5OsSe8Cl6]3− and [Re4Os2Se8Cl6]2−, respectively. They were isolated as salts of the compositions Cs3[Re5OsSe8(OH)6] · 11H2O (I), K3[Re5OsSe8(OH)6] · 7H2O (II), and K2[Re4Os2Se8(OH)6] · 3H2O (III). The protonation of the terminal OH ligands of [Re5OsSe8(OH)6]3− in an aqueous solution resulted in crystallization of a neutral complex [Re5OsSe8(H2O)3(OH)3] · 12H2O (IV). The compounds have been characterized by single-crystal X-ray diffraction analysis. The luminescence properties of [Re5OsSe8(OH)6]3− and [Re4Os2Se8(OH)6]2− were studied. In addition, the electronic structures of the complexes were elucidated by DFT calculations.  相似文献   

18.
Complexation of cobalt(II) and nickel(II) with thiocyanate ions has been studied by precise spectrophotometry in aqueous and micellar solutions of a nonionic surfactant Triton X-100 of varying concentrations (20–100 mmol-dm–3). With regard to cobalt(II), the formation of [Co(NCS)]+, [Co(NCS)2], and [Co(NCS)4]2– was established. The formation constant of [Co(NCS)4]2–, is increased with increasing concentration of the surfactant, suggesting that the [Co(NCS)4]2– complex is formed in micelles. In contrast, the formation constants of [Co(NCS)]+ and [Co(NCS)2] are remained practically unchanged. On the other hand, with nickel(II), the formation of sole [Ni(NCS)]+ and [Ni(NCS)2] was established in both aqueous and micellar solutions examined, their formation constants being also remained unchanged. Interestingly, no higher complex was confirmed in the nickel(II) system, unlike cobalt(II). The unusual affinity of the [Co(NCS)4]2– complex with micelles will be discussed from thermodynamic and structural points of view.  相似文献   

19.
The [{Mn(H2O)3}2{Re6Se8(CN)6}] · 3.3H2O complex was produced on slow evaporation of an aqueous solution containing the salt of a cluster complex K4Re6Se8(CN)6 · 3.5H2O and a 23-fold excess of Mn2+. The cluster complexes [Re6Se8(CN)6]4– are linked in a crystal into the charged coordination layers [{Mn(H2O)3}4{Re6Se8(CN)6}3]4– 2 through the Mn2+ cations. The Mn2+ cations are coordinated in a layer by three cyano nitrogen atoms of the cluster complexes; the Mn–N bond lengths are 2.13(4) and 2.21(2) Å. Each [Re6Se8(CN)6]4– anion is bonded to three manganese cations Mn(1). The anions are bonded additionally to the Mn(2) cations disordered over two close positions.  相似文献   

20.
The crystal structure of (Me4N)3[WO(CN)4(NCS)]·NaNCS was determined from three-dimensional x-ray diffraction data. The dark blue crystals are monoclinic, space group C2/m, with cell dimensions a=13.105(4), b=12.688(2), c=18.871(3) Å, =100.4(8)°, z=4 and D=1.46 g cm–3. Anisotropic refinement of 1333 observed reflections converged to R=0.068. The [WO(CN)4(NCS)]3– ion is a distorted octahedron with the tungsten atom displaced by 0.35 Å out of the plane formed by the four cyano ligands, towards the oxo ligand. The coordinated thiocyanate ligand is bonded to the tungsten atomvia the nitrogen atomtrans to the oxo ligand. Bond distances found: W–CNav=2.14(3), W–O=1.61(2) and W–NCS=2.23(2) Å. The compound crystallizes as an adduct with an additional thiocyanate anion, ionically bonded to a severely disordered sodium cation. The results correlate with available data from similar complexes.  相似文献   

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