Rb4Mo21Se24 containing Mo12 and Mo15 clusters

Rubidium molybdenum selenide, Rb₄Mo₂₁Se₂₄, crystallizes in the trigonal space group R. Its crystal structure consists of a mixture of Mo₁₂Se₁₄Se₆ and Mo₁₅Se₁₇Se₆ cluster units in a 1:2 ratio. Both units are interconnected through Mo—Se bonds. The Rb⁺ cations occupy large voids between the different cluster units.     

Thiophene hydrodesulfurization on P?Mo, Si?Mo and Ti?Mo catalysts

Studies of the catalysts obtained by supporting P–Mo, Si–Mo and Ti–Mo heteropolyacids on anatase in thiophene hydrodesulfurization have revealed that the presence of HPA in the initial catalysts promotes the formation of the molybdenum state ensuring high reaction rates. A possibility for HPA synthesis when supporting paramolybdate on TiO₂, accounts for the great effect of the support on the properties of the catalyst.

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Mo（Ⅵ）－PAN与Mo（Ⅵ）－PAR体系的极谱性质对比研究

本文比较了Ｍｏ（Ⅵ）－１－（２－吡啶基偶氮）－２－萘酚（ＰＡＮ）与Ｍｏ（Ⅵ）－４（２－吡啶基偶氮）间苯二酚（ＰＡＲ）的极谱性质，讨论它们在作为吸附波试剂时的优缺点，以求得在选择络合剂时的感性和理性认识．本文还报道了Ｍｏ（Ⅵ）－ＰＡＮ－ＫＢｒＯ３吸附催化波体系，最佳实验条件，０．１ｍｏｌ／ＬＨＡｃ－－ＮａＡｃ，ｐＨ＝４．６，０．０１ｍｏｌ／ＬＫＢｒＯ３，２．５×１０－５ｍｏｌ／ＬＰＡＮ．峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ），检出限１×１０－９ｍｏｌ／Ｌ，线性范围０～６×１０－７ｍｏｌ／Ｌ     

Synthesis and structures of Mo3Se7Te2Br10, Mo3Se7TeI6, and Mo6Te21I22 containing TeX3- (X=Br, I) ligands coordinated to a triangular cluster core

New ternary and quaternary molybdenum cluster chalcohalides were obtained by high-temperature reactions between Mo, chalcogens, and halogens in evacuated ampules. The crystal structures of [Mo3Se7(TeBr3)Br2]2[Te2Br10] (1), [Mo3Se7(TeI3)I2]I (2), and [Mo3Te7(TeI3)3]2(I)(TeI3) (3) were determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of positively charged zigzag chains infinity1 [Mo3Se7(TeX3)X4/2] (X=Br, I), with Te2Br102- and I-, respectively, as counterions. The TeI3- and TeBr3- ions function as bidentate ligands in 1 and 2. In 3, TeI3- is not coordinated to the metal but acts as a counterion to the [Mo3Te7(TeI3)3]+ cluster cation.     

Synthesis and Crystal Structure of the Novel Compound Mg4.5Pr79.5Mo126O312 Containing Mo3, Mo7 and Mo19 Clusters

The synthesis and crystal structure of the novel reduced molybdenum oxide Mg_4.5Pr_79.5Mo₁₂₆O₃₁₂ are presented. This compound crystallizes in the trigonal space group R-3 m with a = 11.3061(2) Å, c = 58.242(1) Å, V = 6447.5(2) Å³, and Z = 1. Refinements yield R(F ²) = 0.0433 and wR(F ²) = 0.0931 for 2827 unique reflections. The structure is built up from alternating slabs made up of molybdenum forming Mo₃, Mo₇ and Mo₁₉ clusters, praseodymium and oxygen atoms, and slabs containing isolated MoO₆ octahedra. The Pr³⁺ cations are localized either within the slabs or at their borderlines to ensure the cohesion between the slabs. Of the six crystallographically independent sites occupy by the Pr³⁺ cations, two of them also contain randomly about 15% and 20% of Mg²⁺ cations while the remaining four are fully occupied by the Pr³⁺ cations.     

Cs6Mo27S31: a novel ternary reduced molybdenum sulfide containing Mo9 and Mo18 clusters

The crystal structure of hexacaesium heptacosamolybdenum hentriaconta­sulfide, Cs₆Mo₂₇S₃₁, consists of a mixture of Mo₉S₁₁S₆ and Mo₁₈S₂₀S₆ cluster units in a 1:1 ratio. The units are connected through Mo—S bonds. Cs⁺ cations occupy large voids between the different cluster units.     

Desorption of99Mo from spent99Mo/99mTc generator

A simple method for desorption and purification of⁹⁹Mo from spent⁹⁹Mo/^99mTc generators is described. The alumina column was washed successively with 0.9% saline water, 35% H₂O₂, and then the⁹⁹Mo was eluted with 2M NH₄OH. Ammonia and residual H₂O₂ were removed by heating the eluate. Finally,⁹⁹Mo solution was passed through a 0.2 m membrane filter to remove precipitated aluminium hydroxide.     

Ag2.54Tl2Mo12Se15: a new structure type containing Mo6 and Mo9 clusters

The novel structure‐type Ag_2.54Tl₂Mo₁₂Se₁₅ (silver thallium molybdenum selenide) is built up of Mo₆Seⁱ₈Se^a₆ and Mo₉Seⁱ₁₁Se^a₆ cluster units in a 1:2 ratio, which are three‐dimensionally connected to form the Mo–Se network. The Ag and Tl cations are distributed in several voids within the cluster network. Three of the seven independent Se atoms and one Tl atom lie on sites with 3.. symmetry (Wyckoff sites 2c or 2d).     

Rb5Mo27Se31, a novel ternary reduced molybdenum selenide containing Mo12 and Mo15 clusters

The crystal structure of Rb₅Mo₂₇Se₃₁, penta­rubidium hepta­cosa­molybdenum hentria­conta­selenium, consists of a mixture of Mo₁₂Se₁₄Se₆ and Mo₁₅Se₁₇Se₆ cluster units in a 1:1 ratio. Both types of cluster are interconnected through inter‐unit Mo—Se bonds. Rb⁺ cations occupy large voids between the different cluster units.     

Cs2Mo15S19: a novel ternary reduced molybdenum sulfide containing Mo6 and Mo9 clusters

The crystal structure of dicaesium pentadecamolybdenum nonadeca­sulfide, Cs₂Mo₁₅S₁₉, consists of a mixture of Mo₆S₈S₆ and Mo₉S₁₁S₆ cluster units in a 1:1 ratio. Both units are interconnected via inter‐unit Mo—S bonds. The Cs⁺ cations occupy large voids between the different cluster units. The Cs and two inner S atoms lie on sites with 3 symmetry (Wyckoff site 12c) and the Mo and S atoms of the median plane of the Mo₉S₁₁S₆ cluster unit on sites with 2 symmetry (Wyckoff site 18e).     

Quantum-chemical calculations of molybdenum chloride clusters Mo13C24, Mo13Cl26, and Mo13Cl30

Quantum-chemical calculations of the structures and thermodynamic stabilities of isomers of molecular clusters of lower Mo chlorides Mo₁₃Cl₂₄, Mo₁₃Cl₂₆, and Mo₁₃Cl₃₀, as well as of the Mo₁₃Cl ₂₆ ^? anion of cuboctahedral or icosahedral structure, have been performed by the DFT B3LYP method with the use of the Lanl2dz basis set for the Mo atoms and the 631G(d) basis set for the Cl atoms. The highest symmetry polyhedra are considered: Mo₁₃Cl₃₀ and Mo₁₃Cl₂₄ have a structure of centered icosahedron and cuboctahedron with bridging Cl atoms sitting atop the midpoints of 30 and 24 edges, respectively. In both cases, calculations lead to a rapid increase in the Mo-Mo distance to the values that are evidence of the absence of metal-metal bonds; hence, the cluster structure, in its classical meaning, is not retained. Both the neutral cluster Mo₁₃Cl₂₆ and the Mo₁₃Cl ₂₆ ^? anion—a symmetric icosahedron, in which Cl ions sit atop the centers of 20 faces and 6 Cl atoms are terminal, and a cuboctahedron, in which 14 Cl atoms are located on the three- and fourfold axes over the centers of molybdenum faces and 12 terminal Cl atoms are located on twofold axes. For both the neutral cluster and the anion, stable structures have been obtained. In both cases, the total energies are lower for the initial icosahedral configuration.     

Phase relations in the system SbVO5-Sb3V2Mo3O21 in solid-state and in the atmosphere of air

It has been established by XRD, DTA and TG methods that phases of solid solution type of MoO₃ in SbVO₅ are formed in the system V₂O₅-MoO₃-a-Sb₂O₄. The Mo⁶⁺ ions are incorporated into the crystal lattice of SbVO₅ instead of both Sb⁵⁺ and V⁵⁺, while the charge compensation occurs by a formation of cation defects (□) at Sb⁵⁺ and V⁵⁺. The phases Sb_{1-6x □ x}V_{1-6x □ x}Mo_10xO₅ are stable in the solid-state up to 690±10°C and the limit of solubility of MoO₃ in SbVO₅ does not exceed 20.00 mol%. This revised version was published online in July 2006 with corrections to the Cover Date.