The Oxalato-Titanium-Containing Tungstophosphate(V) Dimers, [Ti8(C2O4)8P2W18O76(H2O)4]18− and [Ti6(C2O4)4P4W32O124]20−

The oxalato-titanium(IV)-containing, dimeric 18-tungsto-2-phosphate [Ti₈(C₂O₄)₈P₂W₁₈O₇₆(H₂O)₄]^18? (1) and the 32-tungsto-4-phosphate [Ti₆(C₂O₄)₄P₄W₃₂O₁₂₄]^20? (2) are formed upon reaction of the oxalato-titanium complex [TiO(C₂O₄)₂]^2? with the trilacunary Keggin precursor [A-α-PW₉O₃₄]^9? and the hexalacunary Wells–Dawson precursor [H₂P₂W₁₂O₄₈]^12?, respectively. Polyanion 1 consists of two {PW₉} units encapsulating eight titanium centers and connected to each other via two Ti–O–Ti bridges, and crystallizes as a mixed potassium-sodium-lithium salt in the triclinic space group $P{\bar{1}}$ . Polyanion 2 comprises two {P₂W₁₆} units containing each two titanium atoms, and the two half-units are connected via two titanium atoms decorated by two oxalate groups each, and crystallizes as a mixed potassium-lithium salt in the rhombohedral space group $R{\bar{3}}c$ . Polyanions 1 and 2 were characterized in the solid state by single-crystal XRD, FT-IR, and TGA, whereas polyanion 2 was also investigated by ³¹P and ¹⁸³W NMR.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

Crystal and molecular structure and ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate [(OH)2(O)P(C6H3OCH3)(OCH2CH2)2 O(C6H4OCH3)P(O)(OH)2] · 2H2O

Ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate H₄M² · 2H₂O (I) were described. X-ray diffraction analysis for compound I was performed. The crystals are orthorhombic, a = 7.9818(16) ?, b = 30.553(6) ?, c = 9.0559(17) ?, V = 2208.5(8) ?³, Z = 4, space group Pnma, R = 0.0500 over 1372 reflections with I > 2??(I). In I, the H₄M² molecules are combined by hydrogen bonds (HB) with two crystallographically independent H₂O(7) and H₂O(8) molecules to give neutral H₄M² · 2H₂O aggregates. The HB between the phosphoryl and hydroxyl oxygen atoms of the aggregates and the donor O(7)-H??O(8) HB give rise to a layered structure. Conclusions about the Cu(H₂M²) compound structure were drawn based on the X-ray diffraction, DTA, and vibrational spectroscopy data.     

Synthesis and structure of antimony complexes [Ph3AmP] 2 + [Sb2I8 · 2DMSO]2−, [Ph3PrP] 2 + [Sb2I8 · C4H8O2]2−, and [(HOCH2CH2)3NH] 4 + [Sb4I16]4−

The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph₃AmP] ₂ ⁺ [Sb₂I₈ · 2DMSO]^2?, [Ph₃PrP] ₂ ⁺ [Sb₂I₈ · C₄H₈O₂]^2?, and [(HOCH₂CH₂)₃NH] ₄ ⁺ [Sb₄I₁₆]^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.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

Reactivity of the Unsaturated Triosmium Cluster [Os3(CO)8{Ph2PCH2P(Ph)C6H4}(μ-H)] with Thiols

The reaction of the unsaturated cluster [(-H)Os₃(CO)₈{Ph₂PCH₂P(Ph)C₆H₄}] 2 with C₂H₅SH, CH₃CH(CH₃)SH and C₆H₅SH are reported. The reaction of 2 with C₂H₅SH yields the new complexes [Os₃(CO)₈(-SC₂H₅)(¹-SC₂H₅){Ph₂PCH₂P(Ph)C₆H₄}(-H)] 9 and [Os₃(CO)₈)(SC₂H₅)(Ph₂PCH₂P)(Ph)C₆H₄}] 8 in 24 and 57% yields respectively and the known compound [(Os₃(CO)₈)(-SC₂H₅)(-dppm)(-H)] 7 in 5% yield. Compound 9, which exists as two isomers in solution, converts into 8 almost quantitatively in solution at 25°C and more rapidly in refluxing hexane. Compound8 reacts with H₂ at 110°C to give 7 in high yield (86%). Treatment of 2 with propane-2-thiol yields [Os₃(CO)₈{-SCH(CH₃)CH₃}{Ph₂PCH₂P(Ph)C₆H₄}] 10 and [(Os₃(CO)₈{-SCH(CH₃)CH₃}{¹-SCH(CH₃)CH₃}{Ph₂PCH₂P(Ph)C₆H₄}(-H)] 11 in 75 and 3% yields respectively while with C₆H₅SH, [(Os₃(CO)₈(-SC₆H₅)(-dppm)(-H)] 6 is obtained as the only product in 75% yield. In both 8 and 10, the thiolato ligand bridges the Os–Os edge which is also bridged by the metallated phenyl group. The new compounds have been characterized by elemental analyses and spectroscopic methods (IR, ¹H and ³¹P NMR). The molecular structures of 7, 8, 9 and 10 are reported as determined by X-ray diffraction studies.     

从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Crystal Structure of the Octahedral Cs4[Re6S8Br6] · 2H2O Cluster Complex

The octahedral Cs₄[Re₆S₈Br₆] cluster complex was obtained by the hightemperature (850°) reaction of stoichiometric amounts of elemental substances (metallic rhenium, sulfur, bromine) in molten CsBr. Crystal hydrate of Cs₄[Re₆S₈Br₆]· 2H₂O composition was isolated by recrystallization from an aqueous HBr solution. The crystal structure of the hydrate was determined by means of singlecrystal Xray structural analysis. The compound crystallizes in the hexagonal system with space group P6₃/mcm and unit cell parameters a = 9.762(1), c = 18.763(2), V_cell = 1548.5(3)³, Z = 2, d _calc = 5.192 g/cm³.     

Syntheses, Crystal Structures and Characterization of Two Zeotype Crystals of K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62] ·9.5H2O and K4[Cr3O(H2O)3(OOCH)6[H3P2W17Co(H2O)O61]·20H2O

Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.     

PROPIOLATE CLUSTER COMPLEXES (Bu4N)2[Mo6X8(OOC–C≡CH)6] (X = Br,I)

Journal of Structural Chemistry - Two new cluster complexes (Bu4N)2[Mo6X8(OOC–C≡CH)6] (1) (X = Br) and (2) (X = I) are synthesized by the reaction of...     

23-Electron Re6 metal clusters: syntheses and crystal structures of (Ph4P)3[Re6S8(CN)6], (Ph4P)2(H)[Re6Se8(CN)6]·8H2O,and (Et4N)2(H)[Re6Te8(CN)6]·2H2O

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.     

Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN,and [Ph4Sb]+2[ZrCl6]2–

Russian Chemical Bulletin - The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–?MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–?2 MeCN (3), and...     

Synthesis and structures of mercury and cadmium complexes: [Ph4Sb] 2 + [Hg2I6]2−·Ph2Hg, [Ph4Sb] 2 + [E2I6]2− (E = Hg, Cd), and [Ph4Sb] 2 + [Hg4I10]2−

The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2?·Ph₂Hg (I). The [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2? (II) and [Ph₄Sb] ₂ ⁺ [Cd₂I₆]^2? (III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph₄Sb] ₂ ⁺ [Hg₄I₁₀]^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 [Ph₄Sb]⁺ cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg₂I₂ of the [Hg₂I₆]^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 [Cd₂I₆]^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.     

H2C[P(Ph)2AUX]2和HC[P(Ph)2AUX]3(X=I,CI)型配合物的构象和Au (I)-Au(I)相互作用的从头算研究

根据配合物H₂C[P(Ph)₂AUX]₂(X=I,CI)和HC[P(Ph)₂AUX]₃(X=I,CI)的晶体结构对它们进行了从头算研究,在MP2近似水平下得到绕C-P旋转所产生构象的势能曲线,从而揭示AU(I)－AU(I)相互作用. 计算结果表明,在所研究的四个配合物中均存在AU(I)-AU(I)相互作用,该作用较弱,约为10. 0～16. 5kJ/mol,与Schmibaur的实验估计值和Pyykko等对其它模型配合物的计算结果接近.     

[Eu2(o-ClC6H4OCH2COO)6(C12H8N2)2(H2O)2]·(CH3)2SO的晶体结构和荧光光谱

标题配合物Ｍ＝１８９２．０１,单斜晶系,空间群Ｐ２１／ｃ,ａ＝１．２９７５（３）ｎｍ,ｂ＝２．６５９１（９）ｎｍ,ｃ＝１．２１１８（３）ｎｍ,β＝９６．９５（１）°,Ｚ＝２,Ｄｃ＝１．５７７ｇ／ｃｍ３,Ｔ＝２９３（２）Ｋ。最终的偏离因子Ｒ＝０．０５８３。该配合物以二聚体形式存在,通过其中的桥联羧基形成了双核分子。该分子中羧基具有桥联双齿、桥联三齿和单齿三种配位模式,Ｅｕ－Ｅｕ之间的距离为０．４０１９（１）ｎｍ。在７７Ｋ下测得配合物中Ｅｕ（Ⅲ）离子仅有一种格位。５Ｄ０→７ＦＪ（Ｊ＝０～２）跃迁光谱说明Ｅｕ（Ⅲ）离子格位具有Ｃ２对称性。     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^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 SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ 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.     

Interpretation der Absorptionsspektren der Komplexionen [Mo(CN)8]4−, [Mo(CN)8]3−, [W(CN)8]4− und [W(CN)8]3−

Zusammenfassung Die Absorptions- und Reflexionsspektren der Oktocyanokomplexe desMo(IV) undW(IV) sowie die Absorptionsspektren der Oktocyanotomplexe desMo(V) undW(V) werden mitgeteilt. Die Spektren werden unter Zugrundelegung der durch Raman- und IR-spektroskopische Untersuchungen gefordertenD _4d-Symmetrie dieser Verbindungen interpretiert. Die beobachteten Banden niedriger Intensität (log<3) werden Übergängen in einem Termsystem zugeordnet, das für die Konfigurationend ² undd ₁ und die SymmetrieD _4d berechnet worden ist. Banden hoher Intensität (log>3) werden auf Übergänge in antibindende Zustände zurückgeführt, an denen höherep-Zustände des Zentralions sowie Ligandenzustände beteiligt sind. Die erhaltenen Werte des Feldparameters stimmen mit ligandenfeldtheoretischen Erwartungen überein.

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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.

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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.

     

Reaction of Mo(CO)6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2C6H5)3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a=15.359(2), b=18.378(3), c=24.952(2)(A), β=102.268(4)°, V=6882.3(16) (A)3, Mr=1348.34, Z=4, Dc=1.301 g/cm3, F(000)=2832 and μ= 0.424 mm-1. The final R=0.0606 and wR=0.1552 for 9396 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) (A), indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.