The structurally characterised silyl complexes, Os(κ-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 and Os(κ-S2CNMe2)(SiCl3)(CO)(PPh3)2, which have remarkably unreactive Si-Cl bonds

Treatment of Os(κ²-S₂CNMe₂)H(CO)(PPh₃)₂ with HSiMeCl₂ or HSiCl₃ gives in high yield Os(κ²-S₂CNMe₂)(SiMeCl₂)(CO)(PPh₃)₂ (1) or Os(κ²-S₂CNMe₂)(SiCl₃)(CO)(PPh₃)₂ (2), respectively. The crystal structures of both compounds have been determined and the Os-Si distances are 2.3672(10) Å for 1 and 2.3449(12) Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions.     

Arenechromiumtricarbonyl complexes of silyl(germyl)(stannyl)- and silyl(germyl)(plumbyl)methanes including the unexpected formation of arenechromiumtricarbonyldimethylsilanol, (η-C6H5)Cr(CO)3SiMe2OH

Treatment of PhMe₂SiCH₂GeMe₃ (1) with t-BuLi followed by addition of Me₃ECl, E = Sn, Pb, results in the formation of phenylsilyl(germyl)stannyl- and phenylsilyl(germyl)plumbyl-methanes, PhMe₂Si(Me₃Ge)(EMe₃)CH, E = Sn (2), Pb (3). The thermal reaction of 1, 2 and 3 with Cr(CO)₆ yields the corresponding aryl-Cr(CO)₃ analogs, {(η⁶-C₆H₅)Cr(CO)₃}Me₂Si(Me₃Ge)CH₂ (4) and {(η⁶-C₆H₅)Cr(CO)₃}Me₂Si(Me₃Ge)(EMe₃)CH, E = Sn (5), Pb (6). The thermal treatment of 2 with Cr(CO)₆ in a wet THF/di-n-butyl ether mixture results in the formation of the arenechromiumtricarbonyl silanol {(η⁶-C₆H₅)Cr(CO)₃}Me₂SiOH (7) which exhibits amphiphilic character, forming H-bonded chains in the solid state in a head-to-head arrangement of the areneCr(CO)₃ units.     

Synthesis and structures of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O

Single crystals of Cs₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 4H₂O (I) and (NH₄)₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 6H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂]⁴⁻ chains belonging to the crystal-chemical group A₂K⁰²B₂²M₂¹ (A = UO₂²⁺, K⁰² = C₂O₄²⁻, B² = SO₄²⁻, M¹ = NCS⁻) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.     

Reactions of the titanium-carbide species CpTi(μ-Me)(μ-NPi-Pr3)(μ-C)(AlMe2)3

The reaction of CpTi(μ²-Me)(μ²-NPi-Pr₃)(μ⁴-C)(AlMe₂)₃ with ClSnMe₃ and MeO₃SCF₃ affords the species CpTi(μ²-Cl)(μ²-NPi-Pr₃)(μ⁴-C)(μ²-Cl)(AlMe)(AlMe₂)₂1 and CpTi(μ²-Me)(μ²-NPi-Pr₃)(μ⁴-C)(μ²-O₃SCF₃)(AlMe)(AlMe₂)₂2, respectively. Both 1 and 2 have been structurally characterized.     

［La(CH2ClCOO)2(NO3)(phen)(H2O)］n的合成和晶体结构

合成了混合阴离子配合物［La(CH₂ClCOO)₂(NO₃)(phen)(H₂O)］_n。配合物经元素分析、IR、DTA-TG和UV等表征。用X射线单晶结构分析解析了标题配合物的晶体结构，三斜，空间群P1，晶胞参数为a=10.533(2)?，b=13.136(3)?，c=7.776(1)?，α=96.59(1)°，β=95.76(1)°，γ=108.42(2)°，V=1003.3(3)?³，Z=2,Dc=1.940 g/cm³, F(000)=572, μ(Mo Kα)=24.36 cm^-1。     

Crystal structure of metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH and [Cu2(bpy)(H2O)(L-pha)2](NO3)2·H2O

Two metal-organic coordination polymers [Cu(bpy)₂(H₂O)₂](NO₃)₂·4.5C₂H₅OH (1) and [Cu₂(bpy)(H₂O)(L-pha) ₂](NO₃)₂·H₂O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.     

Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPrⁱ)₂ and the complex (²-C₆₀)Os(CO)(PPh₃)₂(CNBu^t) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C₇₀ with the phosphoryl radicals, which were formed directly from C₇₀ and from the radical adducts of ²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Hydrothermal synthesis and crystal structures of new uranyl oxalate hydroxides: α- and β-[(UO2)2(C2O4)(OH)2(H2O)2] and [(UO2)2(C2O4)(OH)2(H2O)2]·H2O

Two modifications of the new uranyl oxalate hydroxide dihydrate [UO₂)₂(C₂O₄)(OH)₂(H₂O)₂] (1 and 2) and one form of the new uranyl oxalate hydroxide trihydrate [(UO₂)₂(C₂O₄)(OH)₂(H₂O)₂]·H₂O (3) were synthesized by hydrothermal methods and their structures determined from single-crystal X-ray diffraction data. The crystal structures were refined by full-matrix least-squares methods to agreement indices R(wR)=0.0372(0.0842) and 0.0267(0.0671) calculated for 1096 and 1167 unique observed reflections (I>2σ(I)), for α (1) and β (2) forms, respectively and to R(wR)=0.0301(0.0737) calculated for 2471 unique observed reflections (I>2σ(I)), for 3. The α-form of the dihydrate is triclinic, space group , Z=1, a=6.097(2), b=5.548(2), , α=89.353(5), β=94.387(5), γ=97.646(5)°, , β-form is monoclinic, space group C2/c, Z=4, a=12.180(3), b=8.223(2), , β=95.817(4), . The trihydrate is monoclinic, space group P2₁/c, Z=4, a=5.5095(12), b=15.195(3), , β=93.927(3), . In the three structures, the coordination of uranium atom is a pentagonal bipyramid composed of dioxo UO₂²⁺ cation perpendicular to five equatorial oxygen atoms belonging to one bidentate oxalate ion, one water molecule and two hydroxyl ions in trans configuration in 2 and in cis configuration in 1 and 3. The UO₇ polyhedra are linked through hydroxyl oxygen atoms to form different structural building units, dimers [U₂O₁₀] obtained by edge-sharing in 1, chains [UO₆]_∞ and tetramers [U₄O₂₆] built by corner-sharing in 2 and 3, respectively. These units are further connected by oxalate entities that act as bis-bidentate to form one-dimensional chains in 1 and bi-dimensional network in 2 and 3. These chains or layers are connected in frameworks by hydrogen-bond arrays.     

Molybdenum(VI) imido complexes: formation of [Mo(NPh)(S2CNR2)3]X and [Mo(NPh)(S2CNR2)2(μ-MoO4)]2 (R?=?Me, Et) from the reaction of [MoO2(S2CNR2)2] and PhNCO under aerobic conditions

Abstract  

Products from the thermolysis of PhNCO and [MoO₂(S₂CNR₂)₂] (R = Me, Et) are highly dependent upon the reaction conditions. When carried out in air, the major products are cations, [Mo(NPh)(S₂CNR₂)₃]⁺, as shown by a crystal structure of [Mo(NPh)(S₂CNEt₂)₃]₂[Mo₆O₁₉]. Under rigorously anaerobic conditions, reaction of two equivalents of PhNCO with [MoO₂(S₂CNR₂)₂] affords [Mo(NPh)₂(S₂CNR₂)₂] as the major product. However, chloroform solutions of the bis(imido) complexes hydrolyze in air to afford [Mo(NPh)(S₂CNR₂)₂(μ-MoO₄)]₂, in which molybdate groups bridge between molybdenum(VI) imido-bis(dithiocarbamate) centers. These results are placed in context of our earlier studies of these reactions that lead to the formation of oxo-disulfide [MoS₂(NPh)(S₂CNR₂)₂] and dimeric molybdenum(V) [MoO(μ-NPh)(S₂CNR₂)]₂ complexes, thus allowing a full picture of these transformations to be established.     

The bis(trifluoroacetate) analogue of the first-generation Grubbs catalyst: Synthesis, X-ray structure, and metathesis activity of [Ru(CF3CO2)(η-CF3CO2)(CHPh)(PCy3)2]

A simple synthesis of [Ru(CF₃CO₂)(η²-CF₃CO₂)(CHPh)(PCy₃)₂] from dimeric [Ru₂(CF₃CO₂)₂(μ-CF₃CO₂)₂(CHPh)₂(PCy₃)₂(μ-H₂O)] is described. The new complex crystallizes in monoclinic system (P2(1)/c space group) with distorted octahedral coordination. The very low metathesis activity of this new ruthenium benzylidene complex demonstrates that substitution of chlorides with trifluoroacetates in [RuCl₂(CHPh)(PCy₃)₂] results in loss of the catalytic activity.     

[Bi2Cl10(H2-Norf)4(H2O)8](H-Norf是诺氟沙星)(英)

The crystal structure of [Bi2Cl10(H2-Norf)4(H2O)8] (1) comprises [H2-Norf]^ cations and [Bi2Cl10]4^- anions, that are loosely associated via H-bonding interactions, as well as water molecules that also participate in H-bonding interactions. Strong blue-fluorescent emission of 1 at solid state is observed at the room temperature. CCDC:238237.     

Oxidative addition of the Mo-Cl bond to the Pt0 complex. Synthesis and structure of Cp′Mo(μ-CO)2(C2Ph2)Pt2(PPh3)2(CO)Cl

A reaction of Cp′Mo(CO)₃Cl(Cp′ = MeC₅H₄) with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic cluster Cp′Mo(μ-CO)₂(C₂Ph₂)Pt₂(PPh₃)₂(CO)Cl (I) as the sole product. According to X-ray diffraction data, complex I contains single Pt-Mo bonds (2.7962(5) and 2.7699(5) ?) but no Pt-Pt bond (Pt…Pt 2.9746(3) ?). The coordinated diphenylacetylene molecule forms two Pt-C σ-bonds (2.054(6) and 2.083(5) ?) and a π-bond to the Mo atom (Mo-C 2.265(6) and 2.272(5) ?; C≡C 1.387(8) ?). Original Russian Text ? A.A. Pasynskii, I.V. Skabitskii, Yu.V. Torubaev, S.S. Shapovalo, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 410–413.     

Synthesis and X-ray crystal structure of the dinuclear copper(I) complex [Cu2((Me-Pk)2En)(PPh3)4](ClO4)2 · 2CHCl3

The new dinuclear copper(I) complex, [Cu₂((Me-Pk)₂En)(PPh₃)₄](ClO₄)₂ · 2CHCl₃ (I), where (Me-Pk)₂En = N,N′-bis(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine), has been synthesized and characterized by elemental analyses, FT-IR, and single-crystal X-ray diffraction method. In this complex, two Cu(PPh₃)₂ units are connected by one (Me-Pk)₂En bridging ligand. The coordination geometry around each copper(I) atom is a distorted tetrahedron formed by two N atoms from (Me-Pk)₂En and two P atoms from the PPh₃ ligands. The distance between two copper atoms is 7.06(1) ?.     

Structure and synthesis of nitrosoruthenium trans -diammines [Ru(NO)(NH3)2Cl3] and [Ru(NO)(NH3)2(H2O)Cl2]Cl·H2O

A DTA study of thermal decomposition of (NH₄)₂[Ru(NO)Cl₅] in helium atmosphere has been carried out, a synthetic procedure for preparation of the trans-diammine complex mer-[Ru(NO)(NH₃)₂Cl₃] (I) with yield ∼70% has been developed. On re-crystallization of I from aqueous solution a trans-aquanitroso complex [Ru(NO)(NH₃)₂Cl₂(H2O)]Cl·H₂O (II) has been isolated. The structures of the compounds have been determined by single crystal X-ray diffraction: space group Pbcn, a = 6.607(1) ? b = 11.255(2) ? c = 9.878(2) ? (I) and space group Ima2, a = 8.3032(3) ?, b = 8.0890(2) ?, c = 15.9192(5) ? II). Original Russian Text Copyright ? 2008 by M. A. Il’in, V. A. Emel’yanov, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 6, pp. 1128–1136, November–December, 2008.     

Synthesis, crystal structure and properties of [Nd(C6NO2H5)3(H2O)2]2n · (nH5O2)(nHgCl5)(2nHgCl4) · (nH2O) with unprecedented polycationic chains

A novel inorganic-organic hybrid complex, [Nd [Nd (C₆NO₂H₅)₃(H₂O)₂]_2n · (nH₅O₂)(nHgCl₅)(2nHgCl₄) · (nH₂O)(1), was obtained by hydrothermal reactions and structurally characterized by X-ray diffraction. The unit cell parameters are as follows: a = 9.579(1), b = 21.462(2), c = 15.801(1) ?, β = 102.339(6)^ℴ, V = 3173.5(5) ?³, Z = 4, space group P2₁/c. The crystal structure analysis reveals that the title complex is characteristic of a novel polycationic [Nd(C₆NO₂H₅)₃(H₂O)₂]_2n ⁶ⁿ⁺ one-dimensional chain-like structure. Photoluminescent investigation shows that the title complex displays strong emission in blue region, which is attributed to the intraligand π-π*-transition of nicotinic ligands. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.45 eV. The article is published in the original.     

Trimetallic ReBiPt complexes containing spiro-bismuth ligands from the reaction of the bis(tri-t-butylphosphine)platinum with Re3(CO)12(μ-BiPh2)(μ-H)2

Pt(P-t-Bu₃)₂ reacts with the bismuthtrirhenium complex Re₃(CO)₁₂(μ-BiPh₂)(μ-H)₂, 1 at 68 °C to give eight complexes PtRe₂(CO)₉P(t-Bu₃)(μ-H)₂, 2, PtRe₃(CO)₁₂P(t-Bu₃)(μ-Ph)(μ-H)(μ₄-Bi), 3, PtRe₃(CO)₁₃P(t-Bu₃)(μ₄-Bi)(μ-H)₂, 4, PtRe₄(CO)₁₆P(t-Bu₃)(μ-H)₂(μ₄-Bi)(μ₃-Bi), 5, Pt₂Re₅(CO)₂₁[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)₂, 6, trans-Pt₂Re₅(CO)₂₂[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)_2,trans-7, cis-Pt₂Re₅(CO)₂₂[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)₂, cis-7, (an isomer of trans-7) and Re₃(CO)₁₃[PtPBu^t₃]₂(μ-H)₂(μ₄-Bi), 8, all in low yields. When 4 was treated with Pt(P-t-Bu₃)₂ at 68 °C, compounds 2, trans-7, cis-7, and Pt₂Re₄(CO)₁₈[P(t-Bu)₃]₂(μ-H)₂(μ₄-Bi)₂, 9 were formed. When 8 was treated with CO at 25 °C, compounds 2, trans-7, 9, and PtRe₃(CO)₉P(t-Bu)₃(μ₃-Bi)(μ₄-Bi₂), 10 were formed. In all of the products both of the phenyl rings from the bridging BiPh₂ ligand of 1 were cleaved from the bismuth atom. Only compound 3 contains a phenyl ligand and that ligand was a bridging ligand across the Pt-Re bond. All of the products, except 10, and the known compound 2, contain spiro, μ₄-Bi ligands. The higher nuclearity complexes 5, 6, trans-7, cis-7, and 9 contain two bismuth ligands. Compound 10 contains three bismuth atoms. Two of the bismuth atoms in 10 are part of an octahedrally-shaped Re₃PtBi₂ cluster. The third bismuth atom is a triply-bridging ligand on the triangular Re₃ face of the cluster. When a mixture of 4 and 8 was heated to 68 °C in the presence of CO, the new compound PtRe₄(CO)₁₇(P-t-Bu₃)(μ-H)₂(μ₄-Bi), 11 was formed. The molecular structures of all of the new complexes were characterized by single-crystal X-ray diffraction analyses.     

Solubility in the CaCl2 + Mg(NO3)2 ? Ca(NO3)2 + MgCl2-H2O system

For the first time solubility at 25 and 50°C is studied in the CaCl₂ + Mg(NO₃)₂ ↔ Ca(NO₃)₂ + MgCl₂-H₂O four-component reciprocal water-salt system in order to determine the feasibility of preparing calcium nitrate and magnesium chloride. Original Russian Text ? K.R. Matveeva, O.S. Kudryashova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 7, pp. 1200–1204.     

[Pb2(TNR)(NO3)2(H2O)]的制备和晶体结构研究

[Pb₂(TNR)(NO₃)₂(H₂O)] was prepared by reaction of the aqueous solution of lead nitrate and magnesium styphnate. The crystal structure of Pb₂(TNR)(NO₃)₂(H₂O)was determined by single crystal diffraction analysis. The crystal is triclinic, space group P1 with crystal parameters a=0.7279(2)nm,b=1.0698(2)nm,c=1.0738(2)nm;α=86.82(1)°,β=89.52(2)°,γ=83.50(2)°;V=0.8295(3)nm³,Z=2,D_c=3.201g·cm^-3, F(000)=716. The final R value is 0.0358.In the crystal structure, one lead ion was represented by nine coor-dination geometry; the other was showed as ten coordination geometry.