C(1)-Phenethyl Derivatives of [closo-1-CB11H12]− and [closo-1-CB9H10]− Anions: Difunctional Building Blocks for Molecular Materials

C(1)-vinylation of [closo-1-CB₉H₁₀]⁻ ( A ) and [closo-1-CB₁₁H₁₂]⁻ ( B ) with 4-benzyloxystyryl iodide followed by hydrogenation of the double bond and reductive deprotection of the phenol functionality led to C(1)-(4-hydroxyphenethyl) derivatives. The phenol functionality was protected as the acetate. The esters were then treated with PhI(OAc)₂ and the resulting isomers were separated kinetically (for derivatives of anion A ) or by chromatography (for derivatives of anion B ) giving the difunctionalized building blocks in overall yields of 9 % and 50 %, respectively. A similar series of reactions was performed starting with anions A and B and 4-methoxystyryl bromide and iodide. Significant differences in the reactivity of derivatives of the two carborane anions were rationalized with DFT computational results. Application of the difunctionalized carboranes as building blocks was demonstrated through preparation of two ionic liquid crystals. The extensive synthetic work is accompanied by single crystal XRD analysis of six derivatives.     

Synthesis and Study of Tetraamminenickel 9-Molybdomanganate [Ni(NH3)4] · H4[MnMo9O32] · 6H2O

Tetraamminenickel 9-molybdomanganate [Ni(NH₃)₄] · H₄[MnMo₉O₃₂] · 6H₂O (zbdI) has been synthesized and studied by thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.5961 Å, b = 11.1609 Å, c = 8.7200 Å, β = 109.23°, V = 1065.59 ų, ρ_calcd = 3.067 g/cm³, Z = 1.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.     

Synthesis and Structure of 6'-Diethylamino-2'-phenacylami nospiro-[isobenzofuran- 1 (3H), 9'- [9H]xanthen]-3-one

1mTRODUCTIONWehavereportedsomenuorancomPoundswithdifferentsubstitutedgroups"~'>.Thispaperdescribesacontinuationofourinvestigationonthenuoranderivatives.ThecrystalstructureofthecomPOundC,zHzsNzo'(I)(whereRl-NEt2,R2=H,R3=NHCHzCoCeHs,R`=H)wasdeterminedbyX-raydiffractionmethod.Inaddition,wealsocomparethetitlecomPOundwithotherfluorancomPounds.2EXPERIMENTAL2.1SynthesisAmixtureof2'-carboxy-4-diethylamino-2-hydrzophenoneandP-hydroxy-acetanilide(molarratio1:l)insulfuricacidwasheated…     

Synthesis and Structure of 5-Amino-6-(4-fluorophenylamino)-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one

The title compound (C18H15FN6OS) has been synthesized and its crystal structure was determined by X-ray analysis. The crystal belongs to monoclinic system, space group P21/n with a = 13.983(10), b = 7.337(5), c = 16.702(12) (A), α = 90, β = 98.277(12), γ = 90°, V = 1696(2)(A)3, Z = 4, Dc= 1.498 g/cm3, Mr = 382.42,μ = 0.224 mm-1, F(000) = 792, the final R = 0.0362 and wR = 0.0878 for 2579 observed reflections with I ＞ 2σ(Ⅰ). In the title compound, the atoms of C(1),C(2), C(3), C(4), C(5), N(1), N(2), N(3), N(4), N(5), N(6), O(1) and S(1) form a fully delocalized system with the average deviation of 0.0307(A). There exists a part of electron delocalization over the planes of Ⅰ (pyrazolo[3,4-d]pyrimidin-4-one moiety), Ⅱ (phenyl moiety) and Ⅲ (p-fluorophenylamine moiety). In the molecule, intermolecular hydrogen bonds between N(6)-H(6)…O(1)and C( 15)-H( 15)…O( 1 ) are observed.     

Synthesis of novel 6-methyl-4-sulfanylfuro[3,4-с]pyridin-3(1H)-ones

Chemistry of Heterocyclic Compounds - Alkylation of 6-methyl-4-thioxo-4,5-dihydrofuro[3,4-c]pyridin-3(1H)-one in an alkaline medium proceeds regioselectively at the sulfur atom to form sulfanyl...     

Synthesis and reduction of 9-(α-nitrophenacylidene)-4-azafluorene

Reaction of 9-phenacylidene-4-azafluorene with acetyl nitrate produces a mixture of geometric isomers of 9-(-nitrophenacylidene)-4-azafluorene. The nitro group splits off upon reduction of the product in the system zinc-ammonia and zinc-acetic acid and on Raney nickel. Proceeding of the Henry retro-reaction has been pointed out.Russian Peoples' Friendship University, Moscow 117918, RussiaTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 342–347, March, 1999.     

Synthesis and structure of neutral π-arene complex (η6-C6H5Me)U(AlCl4)3

A new neutral -arene complex of trivalent uranium, (⁶-C₆H₅Me)U(AlCl₄)₃ (1), was obtained by the reductive Freidel-Crafts reaction. The crystal structure of 1 was determined by single crystal X-ray diffraction analysis. The U atom in 1 is bound to the C₆H₅Me group by the ⁶ mechanism and is linked to the three AICl₄ groups through two g-CI bridges. The coordination of the U atom is a distorted pentagonal bipyramid in which the center of the arene ring is in one apical position, and the bridging Cl atoms occupy the other vertices.Translated from Izvestiva Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 469–472, February, 1996.     

Synthesis and structure of [UO2(SeO4)(C2H4N4)2] · 0.5H2O

The single-crystal X-ray diffraction analysis of [UO₂(SeO₄)(C₂H₄N₄)₂] · 0.5H₂O (I) is performed. The crystals are monoclinic: space group C2/c, Z = 8, a = 19.035(2), b = 7.1326(8), c = 21.477(2) Å, β = 109.683(4)°. The main structural units of the crystal are chains of [UO₂(SeO₄)(C₂H₄N₄)₂]. Compound I belongs to the crystal-chemical group AT³M ₂ ¹ (A = UO ₂ ²⁺ , T³ = SeO ₄ ^2? , M¹ is a cyanoguanidine molecule) of the uranyl complexes. The chains are united into three-dimensional framework through hydrogen bonds involving the oxygen atoms of the selenate and uranyl groups, the nitrogen atoms of cyanoguanidine, and the hydrogen atoms of the cyanoguanidine or water molecules.     

Synthesis and Crystal Structure of 4-(Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane

<正>The title compound 4-(dichloroacetyl)-1-oxa-4-azaspiro[4. 5] decane (CAS number 71526-07-3, C10H15Cl2NO2, Mr= 252.13) was obtained by the reaction of dichloroacetic acid with 1-oxa-4-azaspiro[4. 5] decane. The crystal is of monoclinic, space group P21ln with the unit cell constants: a = 5.9619(4),b= 10.0066(8), c = 20.0986(4) A,β = 90.194(3)°, V= 1199(4) A3,Z = 4, Dc= 1.397 g/cm3, F(000) = 528, μ(MoKα) = 0.522 mm-1, R = 0.0611 and wR = 0.1656 for 1276 observed reflections (I > 2σ(I)). X-ray analysis reveals that the cyclohexyl adopts a chair conformation and the compound is a chiral one.     

Synthesis and Crystal Structure of (E)-[1-Ferrocenyl-2-(4-Chlorophenyl) ethylene]

1INTRoDUCTIoNCurrently,thereisaconsiderableinterestintheinvestigationoforganicandorganometallicmaterialsshowinglargenonlinearopticalresponse.Theirpotentialusehasbeenresearchedindeviceapplicationswhicharerelatedtothetelecommuni-cations,opticalcomputingandopticalinformationprocessing"2i.Onamicroscopiclevel,oneofthemajorphysicalparameterstodecidethenonlinearopticalpropertiesofmaterialsisthemolecularhyperpolarizability,avaluedeterminedbyelectronicandgeometricstructureofmolecule.Thetitlecompoun…     

Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

Synthesis,structure, and luminescence of the octahedral molybdenum cluster [Mo6I8(SC6F4H)6]2−

A new thiolate cluster complex (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] was synthesized by the metathesis reaction of (Bu₄N)₂[Mo₆I₁₄] and HC₆F₄SAg in methylene chloride. According to the X-ray structure determination, the cluster core {Mo₆I₈}⁴⁺ coordinates six thiolate ligands 2,3,5,6-HC₆F₄S^?. The Mo-Mo and Mo-I distances have their usual values. The average Mo-S distance is 2.538(4) Å, and the Mo-S-C angles range from 107 to 109°. Compound (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] both in solid and in solution displays a bright red microsecond luminescence, which is typical of octahedral molybdenum halide complexes.     

Synthesis and crystal structure of the complex [Mg(H2O)2(dmf@CB[6])(bdc)]·DMF·4H2O and the inclusion compound [dmf@CB[6]]·8H2O

The complex [Mg(H₂O)₂(dmf@CB[6])(bdc)]·DMF·4H₂O (1) and the inclusion compound [dmf@CB[6]]·8H₂O (2) were obtained from a mixture of magnesium perchlorate and water (for compound 1) or magnesium oxide and H₂SO₄ (for compound 2), and cucurbit[6]uryl (CB[6]) in the presence of N,N-dimethylformamide (DMF) with the additives of terephthalic or fumaric acid, respectively. X-ray diffraction studies showed that magnesium cation in compound 1 coordinated two oxygen atoms of the CB[6] molecule, one oxygen atom of the terephthalate anion, two molecules of water, and a DMF molecule located inside the cucurbit[6]uryl cavity. When fumaric acid was used instead of terephthalic acid under similar conditions of synthesis, no coordination of magnesium cations to cucurbit[6]uryl molecules took place, rather an inclusion compound of DMF into the macrocyclic cavitand was formed. Compounds 1 and 2 were characterized by X-ray diffraction data, IR spectroscopy, and elemental analysis.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

Synthesis and reactions of 9-hydroxy-(α-alkoxycarbonylalkyl)-4-azafluorenes

The Reformatsky reaction with 4-azafluorenone has given 9-hydroxy-9-(-alkoxycarbonylalkyl)-4-azafluorenes. The course of this reaction with respect to the -haloester used, and the conversion of these hydroxyesters into hydroxy- and ,-unsaturated acids have been examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 81–85, January, 1991.     

Some electrophilic substitution reactions of closo-[1-CB11H12]− and one-boron insertion into nido-7-L-7-CB10H12 (L = H− or Me3N) compounds. Isolation of all three B-substituted closo-Me3N-1-CB11H11 derivatives

Electrophilic deuteration of closo-[1-CB₁₁H₁₂]⁻ in the DCl/D₂O system confirmed the expected order of reactivity on individual skeletal atoms, decreasing in the series B(12) > B(7–11) > B(2–6) > C(1). In contrast, electrophilic B-substitution of closo-[1-CB₁₁H₁₂]⁻ with H₂NOSO₃H is consistent with the preference of the B(7)-substitution to suggest a different mechanism for almost exclusive formation of 7-H₃N-closo-1-CB₁₁H₁₁. 7-Me₃N-closo-1-CB₁₁H₁₁ was isolated along with the remaining 2- and 12-Me₃N-1-CB₁₁H₁₁ isomers as side products of the thermal decomposition of [BH₂(NMe₃)₂]⁺[nido-7-CB₁₀H₁₃]⁻ at 270°C, which is inconsistent with a specific insertion of the BNMe₃ fragment into the open face of nido-[7-CB₁₀H₁₃]⁻. Nevertheless, clean ¹⁰B-insertion was observed in the reactions of Et₃N¹⁰BH₃ with both nido-[7-CB₁₀H₁₃]⁻ and 7-Me₃N-nido-7-CB₁₀H₁₂ to give respectively closo-[1-CB₁₁H₁₂]⁻ and [1-Me₂N-1-CB₁₁H₁₁]⁻ labelled by ¹⁰B exclusively at the B(2) site. Cage rearrangement was observed, however, in the reaction of 7-Me₃N-8-PhCH₂-nido-7-CB₁₀H₁₁ with Et₃NBH₃ under similar conditions to produce only the 1-Me₃N-7-PhCH₂-1-CB₁₁H₁₀ closo-isomer.     

Synthesis and X-ray structure of the osmium carbonyl anion [HOs3(CO)10 · O2C · Os6(CO)20]−

The reaction of [HOs₃(CO)₁₁]⁻¹¹ with [Os₃(CO)₁₀(MeCN)₂] in acetone gives the green-blue anion [HOs₃(CO)₁₀·O₂C·Os₆(CO)₂₀]⁻ (1) amongst several other products; this anion has been structurally characterised by a single crystal X-ray study of its Bu₄P⁺ salt.     

Theoretical study of H2 elimination from [B n H n + 1]− monoanions (n = 6–9, 11)

Transition states of elementary reactions of H₂ molecule elimination from [B _n H _{n + 1}]^? anions (n = 6–9, 11) in which nucleophilic/electrophilic vacancies form at boron atoms have been localized by the density functional theory method (in the B3LYP/6-311++G** approximation). For a series of [B _n H _{n + 1}]^? anions (n = 6–12), the activation barriers to H2 elimination have been compared to consider the possibility of substitution for exopolyhedral hydrogen atoms by the mechanism with the first rate-limiting stage of formation of [B _n H _{n ? 1}]^? (n = 6–12) intermediates with a vacant “bare” vertex of the boron cluster. For the [B _n H _n ]^2?, [B _n H _{n + 1}]^?, and [B _n H _{n ? 1}]^? anions (n = 6–12), the electronic chemical potential μ and Pearson hardness η have been evaluated since these characteristics make it possible to assess the propensity of different reagents to react with each other in terms of the empirical HSAB principle (soft with soft and hard with hard). The application of this principle is exemplified by the interaction of the [B₁₀H₉]^? and [B₁₂H₁₁]^? anions with acetonitrile CH₃CN, furan C₄H₄O, and 18-crown-6.