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1.
Transformations of the complexes CuPc(4-NO2)4, CuPc(4-Br)4(5-NO2)4, (OH)AlRs(4-NO2)4, and (OH)AlPc(4-Cl)4(5-NO2)4 in concentrated sulfuric acid were studied by spectrophotometry. One protonated form of CuPc(4-Br)4(5-NO2)4 and (OH)AlPc(4-NO2)4 and two protonated forms of CuPc(4-NO2)4 and (OH)AlPc(4-Cl)4(5-NO2)4 were detected experimentally and also by ZINDO1 calculations. Step protonation constants of CuPc(4-NO2)4 and (OH)AlPc(4-Cl)4(5-NO2)4 were determined by quantum-chemical calculations and acid-base titration; these complexes can be regarded as weak bases with respect to H2SO4. The kinetics of dissociation of the complexes at the MÄN bonds were studied. The rate of dissociation of the Cu(II) complexes and (OH)AlPc(4-NO2)4 is proportional to [MPc(R) n ] and [H3O+]2. The rate of dissociation of (OH)AlPc(4-Cl)4(5-NO2)4 showed a weak extremal dependence on the composition of the medium, which was explained by change of its structure in 17.0 M H2SO4. The electronic effect of substituents on the reaction center was considered with account taken of a complex mechanism of activation and fine details of the molecular structure of macrocyclic complexes.  相似文献   

2.
Thermal Behaviour of the Mixtures Na2S? P4S10 and Na4Ge4S10? P4S10 of the System Na2S? GeS2? P4S10 The mixtures of Na2S? P4S10 and Na4Ge4S10? P4S10 were investigated by DTA and DSC. In the system Na2S? P4S10 the congruently melting compounds Na3PS4 and (NaPS3)x and the peritectic phase Na4P2S7 were found. The IR-spectra are given. Glassy, anhydrous and hydrated Na4Ge4Sl0 were prepared and thermochemically characterized. The section Na4Ge4S10? P4S10 is not quasibinary, the mixed cage-anion Ge4?xPxS10(4?x)? thus cannot be prepared by heating and annealing mixtures of Na4Ge4S10 and P4S10.  相似文献   

3.
The vibrational and electronic spectra as well as the magnetic properties of the ion [Co(NH3)4]2+are given and discussed. [Co(NH3)4](ReO4)2 crystallizes cubically and is isostructural with the compounds [Zn(NH3)4](ReO4)2, [Zn(NH3)4](MnO4)2, [Cd(NH3)4](ReO4)2, [Cd(NH3)4](MnO4)2, [Zn(NH3)4]- (OsO3N)2 and [Cd(NH3)4](OsO3N)2.  相似文献   

4.
The thermal stability of α-H4Ru4(CO)12, H4Ru4(CO)10P2, H4Ru4(CO)9P3, H4Ru4(CO)8P4 (where P=triphenylphosphine) has been investigated by differential scanning calorimetry and by thermogravimetric analysis under argon dynamic atmosphere.The TG curves of the triphenylphosphine substituted derivatives of α-H4Ru4(CO)12 suggest the release of the carbonyl and of the phenyl groups through a not well-defined pattern and overlapping decomposition reactions up to the retention of phosphorus in the residue, while α-H4Ru4(CO)12 decomposes to metallic ruthenium. The decomposition heat of α-H4Ru4(CO)12 and the isomerization heat of H4Ru4(CO)8P4 have been evaluated.  相似文献   

5.
Tetrapnictidotitanates(IV) M4TiX4 (M = Sr, Ba; X = P, As), hierarchical Derivatives of the KGe Structure K4□Ge4 The four new tetrapnictidotitanates(IV) Sr4TiP4, Sr4TiAs4, Ba4TiP4 and Ba4TiAs4 are synthesized from the binary pnictides MX (M = Sr, Ba and X = P, As) and elementary titanium in tantalum ampoules. The compounds are isotypic and isoelectronic with Ba4SiAs4 (space group P4 3n (no. 218); cP72; Z = 8; Sr4TiP4: a = 1259.0(1) pm; Sr4TiAs4: a = 1288.3(4) pm; Ba4TiP4: a = 1316.6(2) pm; Ba4TiAs4: a = 1346.9(2) pm). The transition metal compounds form cubic, metallic reflecting crystals (Sr4TiP4 (green); Sr4TiAs4 (silver coloured); Ba4TiP4 (silver coloured); Ba4TiAs4 (violet). They are semiconducting and very sensitive against air and moisture. The structure is a hierarchical derivative of Cr3Si (A15) and KGe type: Cr6Si2 ? (□Ge4K4)6(□Ge4K4)2 ? (TiX4M4)6(TiX4M4)2, where Ti occupies the positions of the Cr3Si structure, and the alkaline-earth metal and pnicogen atoms occupy the positions of the KGe structure. Therefore, Ti is surrounded by four X and four more distant M atoms forming a heterocubane. The mean bond lengths are: d (Ti? P) = 238.0(5) pm; 307 ? d(Sr? P) ? 333 pm; d (Ti? As) = 245.9(4); 313 ? d(Sr? As) ? 341 pm; d (Ti? P) = 240.5(5); 324 ? d(Ba? P) ? 348 pm; d (Ti? As) = 248.3(3) pm; 331 ? d(Ba? As) ? 355 pm.  相似文献   

6.
The preparations of (NH4)2HAl2OF7, (NH4)H2AlOF4, (NH4)2HGa2OF7·3.5H2O and (NH4)2HGaOF4 are described. IR spectra suggest the presence of MOMO chains in these compounds. On isothermal heating at 180°C (NH4)H2AlOF4 decomposes to give (NH4)HAlOF3, and at 150°C (NH4)2HGaOF4 yields (NH4)H2GaOF4. At 18°C (NH4)2HGa2OF7·3.5H2O yields the anhydrous compound.  相似文献   

7.
The reaction of S4N4Cl2 with CH3OH gives S4N4(OCH3)2, a simple dimethoxoderivative of S4N4. Its overall geometry is analogous to other compounds of the S4N4X2 type. The chlorination of S4N4(OCH3)2 leads to the oxidation of one sulfur atom to SVI and CH3OS4N4(O)Cl is formed. The compounds were characterized by ir spectroscopy and their crystal structures were determined from single crystal diffraction data collected at ?153°C. The presence of SVI in the molecule of CH3OS4N4(O)Cl is manifested by a marked shortening of the bonds formed by this atom as compared with S4N4Cl2 and S4N4(OCH3)2.  相似文献   

8.
CF3SO2N?SCl2 reagiert mit (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 oder (C5H10)S[NSi(CH3)3]2 unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S4N4-Derivaten S4N4(NSO2CF3)2(CH3)4 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna21 mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, dx = 1,815 g cm?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF3SO2N? SCl2 reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S4N4-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF3SO2N?SCl2 reacts with (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 or (C5H10S[NSi(CH3)2]2 under elimination of (CH3)3SiCl to yield the eight-membered S4N4 derivatives S4N4?NSO2CF3)2(CH3)4, 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna21 with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, dx = 1.815 g cm?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF3SO2N=SCl2 reacts with trimethyl tin-containing S? N compounds to the known CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 and dimethyl tin dichloride.  相似文献   

9.
Vibrational Spectra of β-P4S5 and P4S7 The vibrational spectra of the solid and liquid cage compounds β-P4S5 and P4S7 have been recorded. The assignments of the frequencies are proposed mainly based on polarization data. β-P4S5 decomposes during melting into P4S3 α-P4S7 and β-P4S6. Molten α-P4S7 dissociates to some extent into β-P4S6 and sulphur. An association of β-P4S6 with α-P4S7 is discussed for the molten state. All reactions in molten P4S7 are reversible.  相似文献   

10.
The crystal structures of Na4SiO4 and Na4GeO4 are isotypic, despite a difference in coordination numbers: in Na4SiO4 only one of the four symmetrically independent sodium atoms is four coordinated, in Na4GeO4 two of them are.
Vergleich der Kristallstrukturen von Natriumorthosilikat, Na4SiO4, und Natriumorthogermanat, Na4GeO4 (Kurze Mitteilung)
Zusammenfassung Die Kristallstrukturen von Na4SiO4 und Na4GeO4 sind isotyp, trotz eines Unterschiedes in den Koordinationszahlen: im Na4SiO4 ist nur eines der symmetrisch unabhängigen Natriumatome vierfach koordiniert, während es im Na4GeO4 derer zwei sind.
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11.
Five silver(I) complex of 4-amino-3,5-dipropyl-4H-1,2,4-triazole (4-NH2-3,5-Pr2tz) or 4-amino-3,5-dibutyl-4H-1,2,4-triazole (4-NH2-3,5-Bu2tz), namely [Ag2(4-NH2-3,5-Bu2tz)2(NO3)2] (1), [Ag4(4-NH2-3,5-Pr2tz)6(NO3)2](NO3)2 (2), [Ag4(4-NH2-3,5-Pr2tz)6](ClO4)4 (3), [Ag4(4-NH2-3,5-Pr2tz)6](CF3SO3)4 (4) and [Ag4(4-NH2-3,5-Bu2tz)6](BF4)4 (5), have been prepared and structurally characterized by X-ray single crystal diffractions. Based on the structural data, a possible mechanism for the formation of Ag4tz6 cluster has been proposed, involving the formation of a dimer of dimer—(Ag2tz2)2, followed by the replacement of counterions by two additional triazoles.  相似文献   

12.
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated.  相似文献   

13.
Due to its high hydrogen density (14.8 wt %) and low dehydrogenation peak temperature (130 °C), Zr(BH4)4 ? 8 NH3 is considered to be one of the most promising hydrogen‐storage materials. To further decrease its dehydrogenation temperature and suppress its ammonia release, a strategy of introducing LiBH4 and Mg(BH4)2 was applied to this system. Zr(BH4)4 ? 8 NH3–4 LiBH4 and Zr(BH4)4 ? 8 NH3–2 Mg(BH4)2 composites showed main dehydrogenation peaks centered at 81 and 106 °C as well as high hydrogen purities of 99.3 and 99.8 mol % H2, respectively. Isothermal measurements showed that 6.6 wt % (within 60 min) and 5.5 wt % (within 360 min) of hydrogen were released at 100 °C from Zr(BH4)4 ? 8 NH3–4 LiBH4 and Zr(BH4)4 ? 8 NH3–2 Mg(BH4)2, respectively. The lower dehydrogenation temperatures and improved hydrogen purities could be attributed to the formation of the diammoniate of diborane for Zr(BH4)4 ? 8 NH3–4 LiBH4, and the partial transfer of NH3 groups from Zr(BH4)4 ? 8 NH3 to Mg(BH4)2 for Zr(BH4)4 ? 8 NH3–2 Mg(BH4)2, which result in balanced numbers of BH4 and NH3 groups and a more active Hδ+ ??? ?δH interaction. These advanced dehydrogenation properties make these two composites promising candidates as hydrogen‐storage materials.  相似文献   

14.
New Phosphido-bridged Multinuclear Complexes of Ag and Zn. The Crystal Structures of [Ag3(PPh2)3(PnBu2tBu)3], [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2, PnPr3), [Ag4(PPh2)4(PEt3)4]n, [Zn4(PPh2)4Cl4(PRR′2)2] (PRR′2 = PMenPr2, PnBu3, PEt2Ph), [Zn4(PhPSiMe3)4Cl4(C4H8O)2] and [Zn4(PtBu2)4Cl4] AgCl reacts with Ph2PSiMe3 in the presence of tertiary Phosphines (PnBu2tBu, PMenPr2, PnPr3 and PEt3) to form the multinuclear complexes [Ag3(PPh2)3(PnBu2tBu)3] 1 , [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2 2 , PnPr3 3 ) and [Ag4(PPh2)4(PEt3)4]n 4 . In analogy to that ZnCl2 reacts with Ph2PSiMe3 and PRR′2 to form the multinuclear complexes [Zn4(PPh2)4Cl4(PRR′2)2] (PRR′2 = PMenPr2 5 , PnBu3 6 , PEt2Ph 7 ). Further it was possible to obtain the compounds [Zn4(PhPSiMe3)4Cl4(C4H8O)2] 8 and [Zn4(PtBu2)4Cl4] 9 by reaction of ZnCl2 with PhP(SiMe3)2 and tBu2PSiMe3, respectively. The structures were characterized by X-ray single crystal structure analysis. Crystallographic data see “Inhaltsübersicht”.  相似文献   

15.
Five silver(I) adducts of 4-amino-3,5-diethyl-4H-1,2,4-triazole (4-NH2-3,5-Et2-tz) or 4-amino-3,5-dimethyl-4H-1,2,4-triazole (4-NH2-3,5-Me2-tz), namely [Ag4(4-NH2-3,5-Et2-tz)6](ClO4)4 (1), [Ag(4-NH2-3,5-Et2-tz)2] n ·n(ClO4) (2), [Ag4(4-NH2-3,5-Et2-tz)6](CF3SO3)4 (3), [Ag4(4-NH2-3,5-Me2-tz)6](ClO4)4·4H2O (4) and [Ag4(4-NH2-3,5-Me2-tz)6](CF3SO3)4·2H2O (5), have been prepared and structurally characterised by X-ray single crystal diffraction. Two types of Ag4tz6 cluster have been observed in the structures of compound 1, 3, 4 and 5, which is rationalised based on the minimisation of the steric repulsions between the substituents on the 3,5-positions of triazole ring. Compound 2 displays an infinite chain structure and may be an intermediate or a minor product in the preparation.  相似文献   

16.
Reaction of Mo(CO)(η2‐C2Ph2)24‐C4Ph4) and Me3NO in acetonitrile solvent affords Mo(NCMe)(η2‐C2Ph2)24‐C4Ph4) 1 . Compound 1 reacts with trimethylphosphine to produce Mo(PMe3)(η2‐C2Ph2)24‐C4Ph4) 2 , or reacts with diphenylacetylene to produce (η5‐C5Ph5)2Mo 3 and Mo(η2‐O2CPh)(η4‐C4Ph4H)(η4‐C4Ph4) 4 . The molecular structures of 1, 2 and 4 have been determined by an X‐ray diffraction study.  相似文献   

17.
Syntheses and Crystal Structures of [( t -Bu4Sb4)Fe(CO)4], [( t -Bu4Sb4)Mo(CO)5], and [( t -Bu3Sb4)Mo(η5-C5Me5)(CO)3] t-Bu4Sb4 reacts with Fe2(CO)9 to form [(t-Bu4Sb4)Fe(CO)4] ( 1 ). [(t-Bu4Sb4)Mo(CO)5] ( 2 ) is formed from (thf)Mo(CO)5 and t-Bu4Sb4. [(t-Bu3Sb4)Mo(η5-C5Me5)(CO)3] ( 3 ) is a product of the reaction of t-Bu4Sb4 with [(η5-C5Me5)Mo(CO)3]2. The crystal structures of 1–3 are reported.  相似文献   

18.
Infrared and Raman Studies of the Na4SnO4, Na4PbO4, and K4SnO4 phases The vibrational spectra of the Na4SnO4, Na4PbO4, and K4SnO4 phases have been studied for the first time. They characterize isolated tetrahedral XO4 groups. The assignments of the i.r. and Raman frequencies have been made by a factor group analysis. The force constants, calculated for K4SnO4 using the obtained spectroscopic data, show the covalent character of the Sn? O bond.  相似文献   

19.
Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S5N5)4[As8Cl28] · 2 S4N4 Whereas P4O10 does not react with (NSCl)3, the oxides As2O3, Sb2O3, and Bi2O3 react under formation of (S5N5)4[As8Cl28] · 2 S4N4, S5N5[SbCl6] and a mixture of S4N5[BiCl4] and S4N4Cl[BiCl4], respectively. The products were characterized by their IR spectra. The crystal structure of (S5N5)4[As8Cl28] · 2 S4N4 was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 21c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S5N5 cations, octameric anions [As8Cl28]4? and S4N4 molecules. The S5N5 ions and the S4N4 molecules show positional disorder, which very probably is of dynamical type for the S5N5 ion. The [As8Cl28]4? ions can be described as a (so far unknown) [As4Cl16]4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl3 molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.  相似文献   

20.
The electronic structures of the tetrahedral molecules P4, Be4(OAc)6O, [PtMe3Cl]4, [Cu I As Me3]4, [Tl OR]4, [Li Me]4 and B4 are discussed using a simple topological equivalent(-)orbital approach.
Zusammenfassung Die Elektronenstrukturen der tetraedrischen Moleküle P4, Be4(OAc)6O, [PtMe3Cl]4, [Cu I As Me3]4, [Tl OR]4, [Li Me]4 und B4 werden diskutiert unter Benutzung einer einfachen Näherung topologisch äquivalenter Orbitale.

Résumé Les structures électroniques des molécules tétraédriques P4, Be4(OAC)6O, [PtMe3Cl]4, [Cu I As Me3]4, [Tl OR]4, [Li Me]4 et B4 sont discutées en usant d'une approche simple par des orbitales équivalentes topologiques.
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