O-Halogensilyl-N,N-bis(trimethylsilyl)hydroxylamine – Synthese,Kristallstruktur und Reaktionen

O-Halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines – Synthesis, Crystal Structure, and Reactions The substitution of halogenosilanes on lithiated N,O-bis(trimethylsilyl)-hydroxylamine in the molar ratio of 1 : 1 occurs on the oxygen atom. The O-halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines were prepared: RSiF₂ON · (SiMe₃)₂ (R = CMe₃ 1 , CHMe₂ 2 , CH₂C₆H₅ 3 , C₆H₂(CMe₃)₃ 4 ), RR′SiFON(SiMe₃)₂ (R = CMe₃, R′ = C₆H₅ 5 ; R = Me, R′ = C₆H₅ 6 ; R = C₆H₂Me₃, R′ = C₆H₂Me₃ 7 ; R = CH₂C₆H₅, R′ = CH₂C₆H₅ 8 ; R = CHMe₂, R′ = CHMe₂ 9 ; R = CMe₃, R′ = CMe₃ 10 ), RSiCl₂ON(SiMe₃)₂ (R = CMe₃ 11 ; R = Cl 12 ). The reaction of fluorosilanes with lithiated N,O-bis(trimethylsilyl)hydroxylamine in the molar ratio of 1 : 2 leads to the formation of O,O′-fluorosilyl-bis[N,N-bis(trimethylsilyl)hydroxylamines]: RSiF[ON(SiMe₃)₂]₂ (R = CMe₃ 13 ; R = C₆H₅ 14 ). 13 could be prepared in the reaction of 1 with LiON(SiMe₃)₂. Lithiated dimethylketonoxime reacts with 1 to Me₂C=NOSiRF–ON(SiMe₃)₂ [R = CMe₃ ( 15 )]. The first crystal structure of a tris(silyl)hydroxylamine ( 4 ) is shown. The angle at the nitrogen prove a pyramidal geometry.     

Further studies on organonickel compounds: the synthesis of some new alkyl-, acyl- and cyclopentadienyl-derivatives and the crystal structure of trans-[Ni(CH2SiMe3)2(PMe3)2]

The complex [NiCl₂(PMe₃)₂] reacts with one equivalent of mg(CH₂CMe₃)Cl to yield the monoalkyl derivative trans-[Ni(CH₂CMe₃)Cl(PMe₃)₂], which can be carbonylated at room temperature and pressure to afford the acyl [Ni(COCH₂CMe₃)Cl(PMe₃)₂]. Other related alkyl and acyl complexes of composition [Ni(R)(NCS)(PMe₃)₂] (R = CH₂CMe₃, COCH₂CMe₃) and [Ni(R)(η-C₅H₅)L] (L = PMe₃, R = CH₂CMe₃, COCH₂CMe₃; L = PPh₃, R = CH₂CMe₂Ph) have been similarly prepared. Dialkyl derivatives [NiR₂(dmpe)] (R = CH₂SiMe₃, CH₂CMe₂Ph; dmpe = 1,2-bis(dimethylphosphine)ethane, Me₂PCH₂ CH₂PMe₂) have been obtained by phosphine replacement of the labile pyridine and NNN′N′-tetramethylethylenediamine ligands in the corresponding [Ni(CH₂SiMe₃)₂(py)₂] and [Ni(CH₂CMe₂Ph)₂(tmen)] complexes. A single-crystal X-ray determination carried out on the previously reported trimethylphosphine derivative [Ni(CH₂SiMe₃)₂(PMe₃)₂] shows the complex belongs to the orthorhombic space group Pbcn, with a = 14.345(4), b = 12.656(3), c = 12.815(3) Å, Z = 4 and R 0.077 for 535 independent observed reflections. The phosphine ligands occupy mutually trans positions P-Ni-P 146.9(3)° in a distorted square-planar arrangement.     

Silicon-containing esters of α-cyanoacrylic acid: synthesis and properties

A number of cyanoacetates have been synthesized: cyanoacetoxymethyitrimethylsilane (1), cyanoacetoxymethylpentamethyldisiloxane (2), cyanoacetoxyetoxymethylpentamethyldisiloxane (3). They were converted by the Knoevenagel reaction to novel esters of a-cyanoacrylic acid (4–13) containing silicon atoms in the ester groups and having the general formula RCH=C(CN)COOCH₂X (where R=H, 4-MeOC₆H₄, MeCH=CH, 2-furyl; X=SiMe₃, SiMe₂OSiMe₃, CH₂OCH₂SiMe₂OSiMe₃). These compounds are capable of copolymerization with esters of cyanoacrylic acid which are the precursors to adhesives for cold curing.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 949–952, May, 1993.     

Coordination polymers based on [Re6Se8(CN)6]4? cluster anion, lanthanide cations, and tetraatomic alcohol erythritol

By the interaction of aqueous solutions of salts of the [Re₆Se₈(CN)₆]⁴⁻ cluster anion with salts of Nd(III), Tb(III), and Yb(III) lanthanides in the presence of tetraatomic alcohol erythritol (butane-1,2R,3S,4-tetraol) three new compounds are obtained: K[Nd(C₄H₁₀O₄)(H₂O)₄{Re₆Se₈(CN)₆}]·4H₂O (P $ \bar 1 $ \bar 1 space group, a = 11.544 ?, b = 13.643 ?, c = 13.838 ?, α = 111.97°, β = 108.08°, γ = 90.08°) (1); [{Yb₂(C₄H₉O₄)₂ × (H₂O)₂}{Re₆Se₈(CN)₆}]·5H₂O (P $ \bar 1 $ \bar 1 space group, a = 10.308 ?, b = 10.505 ?, c = 11.154 ?, α = 88.21°, β = 81.83°, γ = 78.50°) (2); [{Tb₂(C₄H₉O₄)₂(C₄H₁₀O₄)}{Re₆Se₈(CN)₆}]·4H₂O (P $ \bar 1 $ \bar 1 space group, a = 10.002 ?, b = 10.276 ?, c = 11.762 ?, α = 91.32°, β = 104.01°, γ = 106.02°) (3). The structures of these compounds are the coordination polymers (chain (2) and grids (1 and 3)) with different coordination modes of erythritol to the lanthanide cations.     

Crystal structure of the reaction product of copper(II) nitrate with α-(3,3-Dimethyl-3,4-dihydro-1-isoquinolyl)hydroxy-iminoacetonitrile [Cu3(μ3-OH)(μ-L)3(NO3)2(H2O)] · 2H2O

The coordination compound [Cu₃(μ₃-OH)(μ-L)₃(NO₃)₂(H₂O)] · 2H₂O (I), where L is the α-(3,3-dimethyl-3,4-dihydro-1-isoquinolyl)hydroxyiminoacetonitrile anion, has been synthesized. The crystal and molecular structure of I was determined by X-ray diffraction (Enraf-Nonius CAD4, MoK _α radiation, graphite monochromator, ω-scan mode, 2θ_max = 49.96°, 7673 unique reflections, a = 12.745(3) ?, b = 13.726(3) ?, c = 28.835(6) ?, β = 93.44(3)°, V = 5035.2(17) ?³, Z = 4, space group P2₁/c). In the trimer complex I, the copper atoms are combined by a bridging hydroxy group. The copper atoms are additionally linked pairswise by three tridentate chelating bridging organic anions coordinated to the Cu(II) atoms by the N and O atoms of the deprotonated oxime group and by the N atom of the dihydroisoquinoline moiety. Original Russian Text ? V.I. Sokol, V.V. Davydov, N. Yu. Merkur’eva, E.I. Polyakova, Yu.V. Shklyaev, V.S. Sergienko, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1643–1652.     

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.     

Synthesis of 6α-methyl-16α,17α-cyclohexano-19-norprogesterone from a 19-methyl-6-desmethyl precursor

After prolonged refluxing of 19-tosyloxy-16α,17α-cyclohexanopregn-5-en-3β-ol-20-one (3) with NaI in 2-propanol, the initially formed 19-iodo derivative (4) undergoes supraface migration of the CH₂I group from the C(10) atom to the C(6) atom, probably through involvement of a homoallyl cation. The resulting 6β-iodomethyl-16α,17α-cyclohexano-19-norpregn-5(10)-en-3β-ol (5) was transformed in three steps into 6α-methyl-16α,17α-cyclohexano-19-norprogesterone (6α-methyl-19-nor-D′ ₆-pentarane,8). The transformation of compound5 into the target product8 also gave a side product, a pentarane with aromatic ringA (10), which was isolated and characterized by spectroscopic methods. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1688–1691, September, 1997.     

Bis(citrato)hydroxogermanic(IV) acid dimer [H5O2][Ge(H2Cit)(H2.5Cit)(OH)]2 · 2CH3COOH · 2H2O: Synthesis, properties, and crystal and molecular structure

Bis(citrato)hydroxogermanic(IV) acid was obtained for the first time in the complex [H₅O₂][Ge(H₂Cit)(H_2.5Cit)(OH)]₂ · 2CH₃COOH · 2H₂O (H₄Cit is citric acid). The complex was characterized by chemical analysis, X-ray powder diffraction, TGA, and IR spectroscopy. Complex I was studied by X-ray crystallography. The crystals are triclinic; a = 10.0651(4) ?, b = 10.1918(4) ?, c = 10.5838(4) ?, α = 85.0110(10)°, β = 85.2170(10)°, γ = 86.7670(10)°, V = 1076.50(7) ?³, Z = 1, space group P[`1]P\bar 1, R1 = 0.0353 for 5709 reflections with I > 2σ(I). Complex I is composed of centrosymmetric dimeric complex anions [Ge₂(H₂Cit)₂(H_2.5Cit)₂(OH)₂]⁻, dioxonium cations [H₅O₂]⁺, and acetic acid and water molecules of crystallization. The coordination polyhedron of the Ge atom is a trigonal bipyramid. Its equatorial plane comprises two O atoms of the deprotonated alcohol groups of two ligands H₂Cit (A) and H_2.5Cit (B) and the O atom of the terminal OH group (Ge-O, 1.7585–1.7754 ?; O_eqGe(1)O_eq, 116.26°–127.64°). The axial positions are occupied by the carboxy O atom of the deprotonated carboxylate group of the α branch of ligand A (α-Ge-O(C)(carb), 1.8882(12) ?)) and the carbonyl O atom of the hemiprotonated acetate α branch of ligand B (α-Ge-O(C) 1.9615(12) ?, O(1)Ge(1)O(8) 170.47(5)°). In structure I, the complex dianion, the cation, and acetic acid and water molecules are united through hydrogen bonds into a three-dimensional framework.     

Darstellung und Struktur der Zweikernigen tert-Butyliminovanadium(IV)-Komplexe [(μ?NtC4H9)2V2(CH2CMe3)2X2] (X = OtC4H9, CH2CMe3)

Synthesis and Molecular Structure of the Binuclear tert-Butyliminovanadium(IV) Complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] (X = O^tC₄H₉, CH₂CMe₃) Syntheses of the neopentylvanadium(V) compounds ^tC₄H₉N?V(CH₂CMe₃)_3?n(O^tC₄H₉)_n (n = 0 ( 7 ), 1 ( 6 ), 2) are described. 6 and 7 decompose by irradiation splitting off neopentane and yielding the binuclear diamagnetic neopentylvanadium(IV) complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] [X = O^tC₄H₉ ( 8 ), CH₂CMe₃ ( 11 )]. All compounds obtained are characterized by ¹H and ⁵¹V NMR spectroscopy. 8 has been found by X-ray diffraction analysis to be a binuclear complex with bridging tert-butylimino ligands and a vanadium—vanadium single bond. The complexes ^tC₄H₉N?V(CH₂C₆H₅)(O^tC₄H₉)₂ and [(μ-N^tC₄H₉)₂V₂(CH₂SiMe₃)₂(O^tC₄H₉)₂] ( 10 ) have been also prepared; the crystal structure of 8 and 10 are nearly identical.     

New π ligand N,N,N,N′,N′,N′-hexaallylethylenediaminium (L2+): Synthesis and crystal structures of LBr2 · 2H2O and its cuprocomplexes L[CuII(Br0.45Cl3.55)], L[Cu 4I (Br4.55Cl1.45)], and L[Cu 4I Br6]

The alkylation of ethylenediamine with allyl bromide in the presence of a fourfold (with respect to ethylenediamine) molar amount of NaHCO₃ in acetone with an ethanol admixture (15: 1) affords LBr₂ · 2H₂O (I), where L²⁺ is the N,N,N,N′,N′,N′-hexaallylethylenediaminium cation. Single crystals of complexes L[Cu^II(Br_0.45Cl_3.55)] (II), L[Cu₄^I(Br_4.55Cl_1.45)] (III), and L[Cu₄^IBr₆] (IV) are prepared by ac electrochemical synthesis from an ethanolic solution of LBr₂ · 2H₂O, CuCl₂ · 2H₂O (or CuBr₂) at copper wire electrodes. The crystal structures of compounds I–IV are determined by X-ray diffraction analysis. The crystals of complex I are monoclinic: space group P2₁/n, a = 8.544(3), b = 10.404(3), c = 13.350(4) ?, β = 97.29(3)°, V = 1177.2(6) ?³, Z = 2. The bromine anions in compound I are bonded to the L²⁺ cations and water molecules through hydrogen contacts (E)H…Br (E = O, C) of 2.57(3)–2.86(3) ?. The crystals of compounds II–IV are triclinic: space group P . For II: a = 8.762(4), b = 9.163(4), c = 16.500(6) ?, α = 95.62(4)°, β = 96.39(4)°, γ = 111.46(4)°, V = 1211.4(9) ?³, Z = 2; for III: a = 9.074(4), b = 9.435(4), c = 9.829(5) ?, α = 116.12(4)°, β = 104.14(4)°, γ = 100.22(4)°, V = 692.3(6) ?³, Z = 1; for IV isostructural III: a = 9.084(4), b = 9.404(4), c = 9.869(4) ?, α = 116.31(3)°, β = 104.00(3)°, γ = 100.37(3)°, V = 692.1(5) ?³, Z = 1. Unlike the isolated tetrahedral CuX₄²⁻ anion in structure II, an original chain anion (Cu₄X₆²⁻) _n is observed in the structures of π complexes III and IV. Original Russian Text ? M.M. Monchak, A.V. Pavlyuk, V.V. Kinzhibalo, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 414–419.     

Syntheses of the eight-coordinate NH4[ErIII(Cydta)(H2O)2] · 4.5H2O and (NH4)2[Er 2III (Pdta)2(H2O)2] · 2H2O complexes and their structural investigation

In this work, the title complexes, NH₄[Er^III(Cydta)(H₂O)₂] · 4.5H₂O (I) (H₄Cydta = trans-1,2-cyclo-hexanediamine-N,N,N′,N′-tetraacetic acid) and (NH₄)₂[Er₂^III(Pdta)₂(H₂O)₂] · 2H₂O (II) (H₄Pdta= propylene-diamine-N,N,N′,N′-tetraacetic acid), were prepared, respectively, and their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. Complex I selects a mononu-clear structure with pseudosquare antiprismatic geometry crystallized in the triclinic crystal system with space group $ P\bar 1 $ P\bar 1 and the central Er³⁺ ion is eight-coordinated by the hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.568(3), b = 10.024(3), c = 14.377(4) ?, α = 88.404(4)°, β = 75.411(4)°, γ = 88.332(4)°, V = 1194.2(6) ?³, Z = 1, ρ _c = 1.793 g/cm³, μ = 3.586 mm⁻¹, F(000) = 648, R = 0.0257, and wR = 0.0667 for 4169 observed reflections with I ≥ 2σ(I). Complex II is eight-coordinated as well, which selects a binuclear structure with two pseudosquare antiprismatic geometry and crystallizes in the monoclinic crystal system with space group P2₁/n. The central Er³⁺ ion is coordinated by two nitrogens and four oxygens from one hexadentate Pdta ligand. Besides, two oxygens come from one carboxylic group of the neighboring Pdta ligand and one water molecule, respectively. The crystal data are as follows: a = 12.7576(8), b = 9.3151(6), c = 14.3278(9) ?, β = 96.1380(10)°, V = 1692.93(19) ?³, Z = 4, ρ _c = 2.054 g/cm³, μ = 5.015 mm⁻¹, F(000) = 1028, R= 0.0228, and wR = 0.0534 for 2984 observed reflections with I ≥ 2σ(I).     

Syntheses, structural determination and binding studies of nine-coordinate mononuclear (EnH2)1.5 [ErIII(Ttha)] · 3H2O and (EnH2)[ErIII(Egta)(H2O)]2 · 6H2O

In this work, the title complexes, (EnH₂)_1.5[Er^III(Ttha)] · 3H₂O (I) and (EnH₂)[Er^III(Egta)(H₂O)]₂ · 6H₂O (II), where En = ethylenediamine, H₆Ttha = triethylenetetramine-N,N,N′,N″,N″’,N″′-hexaacetic acid, H₄Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized. Their structures have been characterized by IR spectroscopy and single-crystal X-ray diffraction techniques. The X-ray diffraction reveals that I is nine-coordinated and crystallizes in the monoclinic crystal space group P2/n with cell dimensions a = 17.6058(16), b = 9.6249(9), c = 20.560(2) ?, β = 109.7440(10)°, and V = 3279.1(5) ?³. Compound II is also nine-coordinated and crystallizes in the monoclinic crystal space group P2₁/n with the cell dimensions a = 12.938(6), b = 12.651(5), c = 14.943(6) ?, β = 105.441(5)°, and V = 2357.5(17) ?³. In I, each EnH₂²⁺ cation connects three adjacent [Er^III(Egta)(H₂O)]⁻ complex anions through hydrogen bonds, while in I, there are two types of EnH₂ ²⁺ anions. One is highly symmetrical, forming hydrogen bonds with two neighboring [Er^III(Ttha)]³⁻ complex anions. The other anion connects three adjacent [Er^III(Ttha)]³⁻ complex anions through hydrogen bonds. These hydrogen bonds lead to the formation of 2D ladder-like layer structure.     

Crystal structure of a new mononuclear complex of Mn(II) with a bbbi ligand (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene)

A new mononuclear complex Mn(bbbi)₂(H₂O)₄(ClO₄)₂·(bbbi)₂·(H₂O)₂ 1 (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene) is synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: triclinic, , a = 8.8478(7) ?, b = 15.0550(11) ?, c = 16.4310(12) ?, α = 108.657(7)°, β = 104.044(7)°, Γ = 99.317(7)°, V = 1942.2(3) ?³, Z = 1, final R = 0.0621. Each manganese atom is octahedrally coordinated by four aqua ligands and two nitrogen atoms of two distinct bbbi ligands. The molecule is stabilized by hydrogen bonding and π…π interactions.     

Crystal structures of seven-coordinate (NH4)2[MnII(edta)(H2O)]·3H2O, (NH4)2[MnII(cydta)(H2O)]·4H2O and K2[MNII(hdtpa)]·3.5H2O complexes

The title compounds, (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O (H₄edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O (H₄cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂[Mn^II(Hdtpa)]·3.5H₂O (H₅dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn²⁺ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize in triclinic system in P-1 space group. Crystal data: (NH₄)₂[Mn^II(edta)(H₂O)]·3H₂O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?³, Z = 2, D _c = 1.541 g/cm³, μ = 0.745 mm⁻¹, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH₄)₂[Mn^II(cydta)(H₂O)]·4H₂O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?³, Z = 2, D _c = 1.426 g/cm³, μ = 0.625 mm⁻¹, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K₂[Mn^II(Hdtpa)]·3.5H₂O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?³, Z = 2, D _c = 1.687 g/cm³, μ = 1.006 mm⁻¹, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I). Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X. D. Zhang The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008.     

New nine-coordinate (NH4)3[YbIII(ttha)]·5H2O and eight-coordinate (NH4)[YbIII(pdta)(H2O)2]·5H2O complexes: Structural determination

The (NH₄)₃[Yb^III(ttha)]·5H₂O (I) (H₆ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (NH₄)[Yb^III(pdta)(H₂O)₂]·5H₂O (II) (H₄pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes are synthesized by heat-refluxing and acidity-adjusting methods, and their structures are determined by single crystal X-ray diffraction techniques. These two complexes are all mononuclear structures. The complex I crystallizes in ttha monoclinic crystal system with the P2₁/c space group. The central Yb^III ion is nine-coordinated only by one the ligand, and one non-coordinate carboxyl group is left. The crystal data are as follows: a = 10.321(4) ?, b = 12.744(5) ?, c = 23.203(9) ?, β = 91.082(6)°, V = 3051(2) ?³, Z = 4, D _c = 1.754 g/cm³, μ = 3.150 mm⁻¹, F(000) = 1636, R = 0.0357, and wR = 0.0672 for 6203 observed reflections with I ≥ 2σ(I). The YbN₄O₅ part in the [Yb^III(ttha)]³⁻ complex anion forms a pseudo-monocapped square antiprismatic polyhedron. The complex II is coordinated with one pdta ligand and two water molecules, which form an eight-coordinate structure, and crystallizes in the triclinic crystal system with the P[`1]P\bar 1 space group. The YbN₂O₆ part in the [Yb^III(pdta)(H₂O)₂]⁻ complex anion makes a pseudo-square antiprismatic polyhedron. The crystal data are as follows: a = 9.8923(9)?, b = 10.9627(10) ?, c = 12.2618(11) ?, α = 67.284(5)°, β = 70.956(6)°, γ = 68.741(5)°, V = 1115.97(18) ?³, Z = 2, D _c = 1.843 g/cm³, μ = 4.264 mm⁻¹, F(000) = 618, R = 0.0177, and wR = 0.0409 for 4036 observed reflections with I ≥ 2σ(I).     

Enantiomerically Pure Phosphaalkene–Oxazolines (PhAk‐Ox): Synthesis,Scope and Copolymerization with Styrene

The design of a synthetic route to a class of enantiomerically pure phosphaalkene–oxazolines (PhAk‐Ox) is presented. The condensation of a lithium silylphosphide and a ketone (the phospha‐Peterson reaction) was used as the P?C bond‐forming step. Attempted condensation of PhC(?O)Ox (Ox=CNOCH(iPr)C H₂) and MesP(SiMe₃)Li gave the unusual heterocycle (MesP)₂C(Ph)?CN‐(S)‐CH(iPr)CH₂O ( 3 ). However, PhAk‐Ox (S,E)‐MesP?C(Ph)CMe₂Ox ( 1 a ) was successfully prepared by treating MesP(SiMe₃)Li with PhC(?O)CMe₂Ox (52 %). To demonstrate the modularity and tunability of the phospha‐Peterson synthesis several other phosphaalkene–oxazolines were prepared in an analogous manner to 1 a : TripP?C(Ph)CMe₂Ox ( 1 b ; Trip=2,4,6‐triisopropylphenyl), 2‐iPrC₆H₄P?C(Ph)CMe₂Ox ( 1 c ), 2‐tBuC₆H₄P?C(Ph)CMe₂Ox ( 1 d ), MesP?C(4‐MeOC₆H₄)CMe₂Ox ( 1 e ), MesP?C(Ph)C(CH₂)₄Ox ( 1 f ), and MesP?C(3,5‐(CF₃)₂C₆H₃)C(CH₂)₄Ox ( 1 g ). To evaluate the PhAk‐Ox compounds as prospective precursors to chiral phosphine polymers, monomer 1 a and styrene were subjected to radical‐initiated copolymerization conditions to afford [{MesPC(Ph)(CMe₂Ox)}_x{CH₂CHPh}_y]_n ( 9 a : x=0.13n, y=0.87n; GPC: M_w=7400 g mol^?1, PDI=1.15).     

Synthesis,spectral, catalytic,and thermal studies of vanadium complexes with quadridentate schiff bases

The paper reports the synthesis and characterization of vanadium complexes of N,N′-(±)-trans-bis(2,4-dihydroxyacetophenone)-1,2-cyclohexanediamine (H₂L¹) and N,N′-(±)-trans-bis(2,4-dihyroxy-5-nitroacetophenone)-1,2-chyclohexanediamine (H₂L²). All the complexes were characterized by elemental analysis, magnetic susceptibility measurements, infrared and electronic spectra, and thermogravimetric analysis. The X-ray patterns of the [VO(L¹)] · H₂O (I) and [VO(L²)] · H₂O (II) complexes show the monoclinic system with the unit cell parameters a = 26.1352, b = 11.7149, c = 6.0401 β = 115.38° and a = 29.3787, b = 12.9398, c = 5.9175 β = 96.84°, respectively. The complexes I and II catalyze the oxidation of styrene in the presence of hydrogen peroxide.     

Hydrothermal Synthesis and Structure of Two New Mo(V)-Oxide Phosphates

Two new members of Mo(V) phosphates were synthesized by hydrothermal methods. (enH₂)(enH)[NaMo₁₂O₂₄(OH)₆(HPO₄)₂(H₂PO₄)₆]·(en)₄·20H₂O(1)(en=H₂ NCH₂CH₂NH₂)[HAD-H₂]₂[HAD-H]₂[Zn₃Mo₁₂O₂₄(OH)₆(PO₄)₂(HPO₄)₆]·6H₂O (2) (HAD=H₂N(CH₂)₆NH₂). Compound 1 crystallized in the space group P2(1)/n, a=15.93120(10) Å, b=15.8946(2) Å, c=17.0665(2) Å, V=4316.02(8), =92.9060(10)°, Z=2. Compound 2 crystallized in the space group P(–1) with a=12.3726(3) Å, b=14.1948(3) Å, c=14.2310(4) Å, =72.7100(10), =65.0230(10), =69.5600(10)°, Z=2089.70(9) ų, and Z=1. The structure of 1 consists of sandwich-shaped cluster anion [Na{Mo^V ₆O₁₂(OH)₃(HPO₄)(H₂PO₄)₃}₂]^3– ({Na(Mo ^V ₆ ) ₂ }) held together via intermolecular hydrogen-bonding contacts. For the compound 2, the sandwich-shaped clusters Zn[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂ ({Zn(Mo ^V ₆ ) ₂} are linked by tetrahedrally-coordinated zinc into layers. Organic cations ([H₃N(CH₂)₆NH₃]²⁺ and [H₃N(CH₂)₆NH₂]⁺) are filled in the spaces between lamellas. The layers are held together by a hydrogen-bonded network, which involves the terminal phosphate P-OH groups, as well as organic cations and several waters of solvation.     

Structural determination of new eight-coordinate NH4[EuIII(Cydta)(H2O)2]·4.5H2O and K2[Eu 2III (pdta)2(H2O)2]·6H2O complexes

The NH₄[Eu^III(Cydta)(H₂O)₂]·4.5H₂O (I) (H₄Cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂[Eu₂^III(pdta)₂(H₂O)₂]·6H₂O (II) (H₄pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes are prepared by heat-refluxing and acidity-adjusting methods respectively, and their composition and structures are determined by elemental analyses and single crystal X-ray diffraction techniques. The complex I has a mononuclear structure, crystallizes in the triclinic crystal system with the P[`1]P\bar 1 space group; the central Eu^III ion is eight-coordinated by a hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.653(4) ?, b = 10.041(4) ?, c = 14.405(6) ?, α = 88.469(6)°, β = 74.892(6)°, γ = 88.256(7)°, V = 1207.5(9) ?³, Z = 1, D _c = 1.731 g/cm³, μ = 2.669 mm⁻¹, F(000) = 638, R = 0.0257, and wR = 0.0667 for 3807 observed reflections with I ≥ 2σ(I). The EuN₂O₆ part in the [Eu^III(Cydta)(H₂O)₂]⁻ complex anion forms a pseudo-square antiprismatic polyhedron. The complex II is eight-coordinate as well; it is a binuclear structure that crystallizes in the monoclinic crystal system with the C ₂/c space group; half of the central Eu^III ion is coordinated by two nitrogen atoms from one hexadentate pdta ligand and six oxygen atoms from the same pdta ligand, one water molecule and carboxylic group from the neighboring pdta ligand respectively. The crystal data are as follows: a = 19.866(3) ?, b = 9.1017(12) ?, c = 21.010(3) ?, β = 104.972(2)°, V = 3670.1(9) ?³, Z = 8, D _c = 2.046 g/cm³, μ = 3.710 mm⁻¹, F(000) = 2240, R = 0.0213 and wR = 0.0460 for 4183 observed reflections with I ≥ 2σ(I). Otherwise, the two EuN₂O₆ parts in the [Eu₂^III(pdta)₂(H₂O)₂]²⁻ complex anion form a pseudo-square antiprismatic polyhedron.