bluuebunny/crossref_metadata_2025 huggingface dataset:
Metal(II) Complexes of 1,2,5-Oxadiazole
Authors: Driessen W. L. , Everstijn P. L. A.
Published: March 2015

A series of new coordination compounds is reported with 1,2,5-oxadiazole (ODZ) as the ligand, viz. [M(ODZ)3](SbCl6)2 with M = Mg(II), Mn(U), Fe(II), Co(II), Ni(II), and Zn(II). The metal ions are in a regular octahedral environment of six nitrogen atoms. The ligands function as bidentate bridges between the metal ions.
Montanin-D, a New Furanoid Diterpene of Clerodane Type from Teucrium montanum L.
Authors: Malakov Peter , Papanov Georgi , Mollov Nikola M. , Spassov Stefan L.
Published: March 2015

A new furanoid diterpene of clerodane type, Montanin-D [1], is isolated from the bitter fraction of the arial parts of Teucrium montanum L., spread in Bulgaria. Its structure is established on the basis of spectral evidance and chemical transformations.
Massenspektrometrische Untersuchungen zur Genese von [M—Me] [M-Et] [C7H7]+ und [C7H8]+ aus n-Butyl- und n-Pentylbenzol: Zeitabhängige Nachbargruppeneffekte, Isomerisierungen und kompetitive Wasserstoff-Umlagerungen / Mass Spectrometric Investigations on the Formation of [M-Me] [M-Et] [C7H7]+ und [C7H8]+ from w-Butyl and w-Pentyl Benzenes: Time Dependent Neighbouring Group Participation, Isomerization and Competitive Hydrogen Rearrangements
Authors: Wesdemiotis Chrysostomos , Schwarz Helmut , Borchers Friedrich , Heimbach Heinz , Levsen Karsten , Wesdemiotis Chrysostomos , Schwarz Helmut
Published: March 2015

The details of the elimination of CH3· and C2H5· from the molecular ions of n-butyl and n-pentyl benzenes as well as the formation of C7H7+ and C7H7+ -have been established using a combination of different mass spectrometric techniques. Among these techniques are field ionization kinetics (FIK), collisional activation (CA), unimolecular decomposi-tion of metastable ions (MI), kinetic energy release determinations (Tkin)> appearance potential measurements (AP) as well as high resolution mass spectrometry. The appli-cation of these methods and the investigation of nine 13 carbon and eleven deuterium labelled n-butyl and n-pentyl benzenes clearly demonstrate that 1) the loss of methyl and ethyl from terminal positions of the alkyl chains are accompanied by an interaction with the phenyl ring and 2) the regioselectivity of these processes is time dependent. Contrary to previous conclusions it is shown that hydrogen transfer in the formation of C7H8+ -occurs via five-, six-and seven-membered transition states. The time dependence of the hydrogen exchange reaction preceding the alkene eliminations is discussed in detail.
Reactions of t-Butyl Peresters, XVI Reactions of Diakyl t-Butylperoxy Phosphates and Alkyl t-Butylperoxy Alkylphosphonates with Cycloalkenes in the Presence of Copper Ions
Authors: Sosnovsky George , Karas Gary
Published: March 2015

The reactions of dialkyl t-butylperoxy phosphates (1) and alkyl t-butylperoxy alkylphosphonates (2) with cyclohexene in the presence of a catalytic

amount of copper (I) bromide at 80 °C in benzene afforded the corresponding phosphates (3) and phosphonates (4) in 50 to 70% yield. The analogous reaction of 1 (R = i-C3H7) with cycloheptene also gave the corresponding phosphate (8, n = 3)

in 71% yield. However, phosphorylated cyclopentene (8, n = 1) and cyclooctene (8, n - 4) derivatives could not be isolated because of their thermal instability, and only the corresponding 1,3-cyclopentadiene and 1,3-cyclooctadiene were obtained in 92 and 38% yields, respectively. Thermal decomposition of 3 and 4 in the absence of a solvent at 110-115 °C gave 1,3-cyclohexadiene in 70 to 90% yield. For identification purposes, compounds 3 and 4 were prepared from the corresponding imidazole derivatives 5 and 6 and 2-cyelohexen- l-ol (7).

A mechanism is proposed for the copper ion catalyzed reaction of 1 and 2 with cycloalkenes.
Notizen: Redistribution Reactions of Monoorganothallium Compounds
Authors: Pohl Udo , Huber Friedo
Published: March 2015

Disproportionation of monoorganothallium acetate RT1X2 (X = CH3COO) does not become evident at room temperature since equilibrium concentrations of disproportionation products, R2TIX or TIX3 are too small to be detected, e.g. by NMR spectroscopy (solvent: CD3COCD3/ CH3OH; R = C6H5, CHs). (CH3O)3P, which had been used in the synthesis of Aryl2TlY (Y = CF3COO) from ArylTlYa [1], continuously removes TIX3 from the equilibrium and effects disproportionation of ArylTlX2. In the same way disproportionation of an AlkylTlX2 compound (Alkyl = CH3) could be accomplished for the first time. The exchange of the organic groups is rate determining.
Notizen: N- (Dimethylaminosulfonyl)-hydroxylamin, (CH3)2NSO2NHOH / N-(Dimethylaminosulfonyl )hvdroxylamine, (CH3)2NSO2NHOH
Authors: Oettle Johannes , Brink Klaus , Morawietz Gerd , Backhaus Michael , Boldhaus Michael , Bliefert Claus
Published: March 2015

N- (Dimethylaminosulfonyl)hydroxylamine is obtained from the reaction of dimethylaminosulfonyl chloride with hydroxylamine. This very weak acid has been characterized by IR, 1H NMR, and mass spectra. The alkaline hydrolysis is reported.
Notizen: Tetrakis - difluorooxoschwefelimidatometallate( II), [M(NSOF2)4]2-, (M = Hg, Co, Pd) / Tetrakis-difluorooxosulfurimidatometallates( II), [M(NSOF2)4]2-, (M = Hg, Co, Pd)
Authors: Eisenbarth Rainer , Sundermeyer Wolfgang
Published: March 2015

Tetrakis-difluorooxosulfurimidato-metallates (II), [M(NSOF2)4]2-, (M = Hg, Co, Pd) are prepared from Hg(NSOF2)2, CoCl2 and Pd(CH3COO)2, respectively, by reaction with (C6H5)4PNSOF2 or (C6H5)4AsNSOF2.
Perantimonidogallate und -indate: Zur Kenntnis von Ca5Ga2Sb6 , Ca5In2Sb6 und Sr5In2Sb6 / Ca5Ga2Sb6, Ca5In2Sb6 and Sr5In2Sb6 : the First Perantimonidogallate and -indates
Authors: Cordier Gerhard , Schäfer Herbert , Stelter Michael
Published: March 2015

The new compounds Ca5Ga2Sb6, Ca5In2Sb6 and Sr5In2Sb6 crystallize in the orthorhombic system (space group: Pbam, No. 55) with the lattice constants:

Ca5Ga2Sb6: a = 1402.1(5) pm, b = 1210.6(4) pm, c = 445.2(2) pm;

Ca5In2Sb6: a = 1425.6(5) pm, b = 1213.3(4) pm, c = 457.2(2) pm;

Sr5In2Sb6: a = 1474.9(5) pm, b = 1269.6(4) pm, c = 466.0(2) pm.

In the structures there are anionic E(III)2E(V)6-strings, compensated by the alkaline earth ions. The compounds belong to the Zintl phases
Ein isoliertes cyclisches Thioarsenat(III)-Anion. Darstellung und Struktur von (enH2)3 (As3S6)2 · 6en / An Isolated Cyclic Thioarsenate(III) Anion. Preparation and Structure of (enH2)3(As3S6)2·6en
Authors: Sheldrick W. S. , Kaub J.
Published: March 2015

The thioarsenate(III) (enH2)3(As3S6)2 · 6en 1 (en = ethylenediamine) has been prepared by the reaction of ethylenediamine with As2S3 and its structure established by X-ray structural analysis. 1 contains discrete cyclic As3S6
3- anions with a six-membered As3S3-ring in the chair conformation. The As atoms display a ψ-tetrahedral coordination
Structure of Dibromo(1,2-diaminoethane)palladium(IV)-bis(1,2-diaminoethane)- palladium(II) Tetrakisperchlorate, [Pd(en)2Br2][Pd(en)2](ClO4)4
Authors: Martin R. , Keller H. J. , Müller B.
Published: March 2015

Orthorhombic [Pd(C2H8N2)2Br2][Pd(C2H8N2)][ClO4]4, C8H32Br2Cl4N8O16Pd2, Mr = 890.42, crystallizes in space group Iba2, a = 9.651(2), b = 13.951(8), c = 10.771(2) Å, Z = 2, V = 1412.80 Å3, dc = 2.05 g cm-3, R = 0.0564 for 1545 unique reflections. Data collection: MoKα, λ = 0.71069 Å, room temperature.

The structure is a typical Wolffram’s Salt Analogue (WSA) with infinite stacks of planar [Pd(en)2]2+,4+ complex cations bridged by bromides. The ligands are three-dimensionally ordered. Intra-chain and inter-chain hydrogen bridges link the ligands with the perchlorate counter ions which occupy statistically two different orientations. Diffuse sheets appear together with Bragg reflections for 1 odd layers indicating a thermally activated motion of the bromides in chain direction. This model was confirmed with temperature dependent Weissenberg work
Zur Reaktion aromatischer Phosphanderivate mit Elektronen, III [1, 2] Phosphan-Borane, -Alane und -Gallane / On the Reaction of Aromatic Phosphane Derivatives with Electrons, III [1, 2] Phosphane-Boranes, -Alanes, and -Gallanes
Authors: Kaim Wolfgang
Published: March 2015

The 1:2 molecular complexes formed from 1,4-phenylenebis(dimethylphosphane) and boranes, trialkyl-aluminum and -gallium have been reduced by potassium in THF in the presence of a K+
- complexing crown ether. The bis(borane) complex anion radicals proved to be quite persistent, whereas corresponding aluminum radical complexes could only be observed below 240 K. The bis(trimethylgallium) complex gave gallium metal on reduction with potassium. An ESR spectroscopic comparison with the anion radicals of the free ligand, of corresponding chalcogenides, imines and phosphonium salts demonstrates negligible effects of P-complexation on the π spin distribution but high sensitivity of the 31P coupling constant towards coordination of electrophiles at the basic P(III) centers
Dikationether, 6 [1] Spektroskopische Vergleiche von 9,9′-Oxy-bis(acridinium)- und 9,9′-Thio-bis(acridinium)-Salzen mit anderen 9-substituierten Acridinium-Ionen / Dication Ethers, 6 [1] Spectroscopic Comparisons of 9,9′-Oxy-bis(acridinium)- and 9,9′-Thio-bis(acridinium) Salts with Other 9-Substituted Acridinium Ions
Authors: Maas Gerhard , Singer Berndt
Published: March 2015

9,9′-Oxy-bis(acridinium) salts 2a and 2b as well as the 9,9′-thio-bis(acridinium) salt 2c have been compared with other 9-substituted acridinium salts by 1H NMR, 13C NMR, and UV/VIS spectra. The data show that the bond state of the acridine rings in 2a-c is quite similar to that in 9-(pseudo)halide-substituted acridinium ions, i.e., the aromatic conjugation throughout the heterocyclic system is not disturbed
Phosphinsubstituierte Chelatliganden, XII [1]. Metallinduzierte E/Z-Isomerisierung an Rheniumcarbonyl-Komplexen mit Phosphinothioformamid-und -thioformimidat-Liganden / Phosphine-Substituted Chelate Ligands, XII [1]. Metal-Induced E/Z-Isomerisation of Rheniumcarbonyl Complexes with Phosphino- thioformamide and -thioformimidate Ligands
Authors: Kunze Udo , Bruns Andreas
Published: March 2015

The coordination of tertiary phosphinothioformamides and the isomeric S-alkyl phosphinothioformimidates to BrRe(CO)5 gives the fac-bromotricarbonylrhenium complexes 1a, b and 2a, b with P,S-chelate ligands. Unlike the analogous manganese complexes, the NMR spectra of dissolved 1b and 2a, b show a splitting of the N-alkyl (1H, 13C) and phosphorus signals indicating E/Z isomerisation of the ligands
Structure and Reactivity of Aromatic Polymers/Ruthenium Catalysts
Authors: Ciardelli Francesco , Pertici Paolo
Published: March 2015

Previously prepared (J. Mol. Catalysis 11, 353 (1981)) polystyrene/ruthenium systems have been examined by EXAFS, TEM, IR and Raman spectroscopy. A structure based on small metal clusters bound to the polymer by single ruthenium-arene binding is proposed. The general validity of the approach has been confirmed by preparing a similar product when starting with poly-1- vinylnaphthalene in the place of polystyrene.

Both systems are active for the hydrogenation of a large variety of unsaturated groups such as olefinic double bonds, mononuclear aromatic hydrocarbons, ketones, nitriles, nitroaromatic compounds and oximes. Catalytic activity, chemio- and stereoselectivity are discussed in terms of the proposed structure.
Preparation and Reactions of η3 -Allylcarboxylatoruthenium
Authors: Sano Kenji , Yamamoto Takakazu , Yamamoto Akio
Published: March 2015

Reactions of (1,5-cyclooctadiene)(1,3,5-cyclooctatriene)ruthenium(0) with 3-butenoic acid in the presence of tertiary phosphines, PR3 , afford η3 -allylcarboxylatoruthenium(II) complexes formulated as (PR3)2[xxx](1 (PR3 = PPh3), 2 (PR3 = P(C6H4-p-OCH3)3). The reaction of 1 with carbon monoxide gives the complex (PPh3)2(CO)[xxx] while reaction with Br 2 or I 2 leads to ring closure of the organic ligand to afford 2-butenolide.
Acetate Peroxyl Radicals, ·O2CH2 CO2
-: A Study on the γ-Radiolysis and Pulse Radiolysis of Acetate in Oxygenated Aqueous Solutions
Authors: Schuchmann Man Nien , Zegota Henryk , Sonntag Clemens von
Published: March 2015

Hydroxyl radicals from the radiolysis of N2O/O2 (4:1 v/v)-saturated aqueous solutions have been reacted with acetate ions (10-2M). As measured by pulse radiolysis, the resulting ·CH2CO2
- radicals react with oxygen yielding the corresponding peroxyl radicals, ·O2CH2CO2
- (k = 1.7 x 109 M-1s-1).

These peroxyl radicals decay bimolecularly (2k = 1.5 x 108 M-1s-1) giving rise to the products (G values in brackets) glyoxylic acid (2.7), glycolic acid (0.7), formaldehyde (1.4), carbon dioxide (1.4), organic hydroperoxide (0.7) and hydrogen peroxide (2.5). Oxygen is consumed with a G value of 5.3. Aided by data from pulse radiolysis it is concluded that the intermediate tetroxide formed upon the bimolecular decay breaks down by various routes to yield:

(i) hydrogen peroxide and two molecules of glyoxylic acid (ca. 27%);

(ii) oxygen, glycolic acid and glyoxylic acid (ca. 25%);

(iii) hydrogen peroxide and two molecules of formaldehyde, carbon dioxide and OH- (25%).

These reactions do not involve free radicals as intermediates;

(iv) There is some O⨪
2 (G ≈ 0.5) formed in the decay of the peroxyl radicals, which is attributed to the decay of intermediate oxyl radicals (tetroxide → O2 + 2 ·OCH2CO2
-) by 1,2-H shift, oxygen addition and HO2
· elimination, a reaction sequence which gives rise to glyoxylic acid (10%); (v)

The reaction of O2
⨪ with the organic peroxyl radical yields the hydroperoxide (13%).

Reaction (iii) is a novel peroxyl radical reaction.
Transformations in Thin Solid Layers: The Reversible Polymerization-Depolymerization of 2,6-Di-n-propyl- 1,3,5,7-tetraoxa-2,6-dibora-4,8-octalindiones at Low Temperatures
Authors: Yalpani Mohamed , Klotzbücher E.
Published: March 2015

The course of Aggregation of molecules of the title compound (1b) through different, spectroscopically discernible and chemically identifiable forms of associations could be followed by matrix isolation and thin film infrared and UV-visible spectroscopy. It was found that molecules of 1b in thin films form clusters which at low temperatures interact weakly, probably through the carbonyl oxygens of one and the boron atoms of the neighbouring molecules. On warming to 260 K this association gradually takes the form of more defined chelate bonds, probably with ordered three-dimensional intermolecular structures. Above this temperature spontaneous formation of crystallites of the previously reported ʻhotʼ and ʻcoldʼ modifications was observed. Studies with films of varying thickness indicate an interdependence of crystallite size and lattice energies.
Ein neues borhaltiges Anion mit dem Adamantangerüst CB5 S4/A New Boron-Containing Anion with the Adamantane Skeleton CB5S4
Authors: Wolfer Klaus , Hausen Hans-Dieter , Binder Herbert
Published: March 2015

Hydroboration of CS2 with NaB3H8 yields the new compound Na[CH2(BH 2)5S4 ], isolated as the tri-dioxanat. The anion has the adamantane skeleton CB5S4 .The crystal structure of the analog-ous compound (C6H5)4P[CH2 (BH2)5 S4 ] was determined from diffractometer data and refined to R = 0.043. The tetragonal unit cell (space group P4/n) contains two formula units (a = b = 1351.7 pm; c = 790.0 pm).
Tetrahalogenotellurate(II): Synthese und Kristallstrukturen von Verbindungen mit den Ionen TeX4
2- (X = Cl, Br, I)/Tetrahalotellurates(II): Syntheses and Crystal Structures of Compounds with TeX4
2- Ions (X = Cl, Br, I)
Authors: Pohl Siegfried , Saak Wolfgang , Krebs Bernt
Published: March 2015

The compounds [(C6H5)4As]2 TeCl4 (1), [(C2H5)4 N]2 TeBr4 · CH3CN (2), and [(C2H5)4N]2TeI4 (3) were prepared by the reaction of Te, X2 , and excess (C2H5)4NX (X = Br, I) in acetonitrile solution or by heating of [(C6H5)4 As]2TeCl6 , Te, and (C6H5)4 ASCl for several hours in the same solvent.

The structures of 1-3 were determined from single crystal X-ray data.

1 crystallizes in the monoclinic space group P21/n with a = 1061.8(2), b = 1614.2(3), c = 1341.7(3) pm, β = 94.21° and Z = 2; 2: tetragonal, P4/mmm, a = 1039.7(2), c = 690.5(1), Z = 1; 3: tetragonal, I4/mmm, a = 1061.7(2), c = 1342.8(4), Z = 2. In 1-3 Te(II) exhibits a square planar coordination. The Te -CI, Te -Br, and Te-I bond lengths were found to be 260.7 (mean), 275.3, and 298.5 pm, respectively.
Darstellung und Struktur einiger η5 -Cyclopentadienyldicarbonyleisenbismut-Verbindungen Cp(CO)2 FeBiX2 mit fünffach koordiniertem Bismutatom/Synthesis and Structure of Some η5 -Cyclopentadienyldicarbonylironbismuth Compounds Cp(CO)2 FeBiX2 with Five-Coordinated Bismuth Atoms
Authors: Wieber Markus , Wirth Dieter , Burschka Christian
Published: March 2015

The synthesis and the spectroscopic properties of the title compounds Cp(CO)2FeBiX2 (with X = SC(S)NEt 2 and SC(S)OMe) are described. The crystal structure of Cp(CO)2FeBi[SC(S)NEt2]2 was investigated by an X-ray analysis.
Umsetzungen von Metall-und Metalloidverbindungen mit mehrfunktionellen Molekülen, XXXIX 1,3-Diaza-2-sila-cyclopentan-4,5-dione/Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules, XXXIX 1,3-Diaza-2-sila-cyclopentane-4,5-diones
Authors: Maringgele Walter
Published: March 2015

N,N′-Diorganyl-oxalic acid diamides react with bis(diethylamino)dimethylsilane to yield the 1,3-Diaza-2-sila-cyclopentane-4,5-diones 1-9. The compounds were characterized by elemental analyses and spectroscopic data (NMR: 1H, 13C, 29Si, 14 N; MS; IR).
Antagonists of the Luteinizing Hormone Releasing Hormone with Emphasis on Amino Acids in Position Five
Authors: Folkers Karl , Bowers Cyril Y. , Yin-Zeng Liu , Shao-Bo Xiao , Shieh Hong-Ming , Ji-Yu Chu
Published: March 2015

Seventeen analogs of the luteinizing hormone releasing hormone (LHRH) have been synthesized, bioassayed, and compared for antiovulatory activity (AOA) in rats. The emphasis of design was replacement of Tyr5 of LHRH. Position 5 has not been extensively studied. [N-Ac-D-2-Nal1 , D-pClPhe2 , D-3-Pal3 , D-Arg6 , D-Ala10 ]-LHRH was the baseline for new designs. Comparison of the AOA's of the 17 analogs with the baseline revealed the two peptides with Phe5 and 3-Pal5 had equivalent AOA's, and were the best of the 17, and about 45% more potent than the baseline. Analogs with pClPhe5 , oClPhe5 , α-MepClPhe5 , 2-Nal5 , Trp5 , and His5 were less potent than the Phe5 -and 3-Pal5 -analogs. Based on the Phe5 -analog, eight other analogs were synthesized with changes in positions 1, 2, 3 and 7 and although none were better than the baseline, 5/8 showed 20-60% AOA's at 250 ng and revealed optimum positions for new designs.
A New Metabolite from Aspergillus quadrilineatus
Authors: Ahmad Viqar Uddin , Suitana Viqar
Published: March 2015

From the mycelium of the fungus Aspergillus quadrilineatus, a new pigment 7-methoxyaverufin has been isolated besides mannitol, sterigmatocystin, versicolorin, ergosterol, and averufin.
Ein tetrameres Zirconocen und seine Spaltung zu Chloro-bis(η5 -cyclopentadienyl)-trimethylsilyl-zirkonium(IV) oder Bis[bis(η5 -cyclopentadienyl)-trimethylstannyl-zirkonium(III)] / Tetrameric Zirconocene and its Cleavage to Chloro-bis(η5-cyclopentadienyl)-trimethylsilyl-zirconium(IV) or Bis[bis(η5 -cyclopentadienyl)-trimethylstannyl-zirconium(III)]
Authors: Kopf Hartmut , Klapotke Thomas
Published: March 2015

A tetrameric zirconocene, [Cp2Zr]4, was prepared by reducing Cp2ZrH2 with red or white phosphorus, with grey arsenic or with antimony in toluene. The tetramer reacts with adequate amounts of Me3SiCl to give Cp2Zr(SiMe3)Cl, but with Me3SnCl to give [Cp2Zr(SnMe3)]2, Cp2ZrCl2, and Sn2Me6. Reaction with Ph2PCl yields Cp2ZrCl2 and P2Ph4.
Über ein Ikosaborat-Ion in hydratisierten Kalium- und Natriumkupferpolyboraten / On an Icosaborate Ion in Hydrated Potassium and Sodium Copper Polyborates
Authors: Heller Gert , Pickardt Joachim
Published: March 2015

K5H{Cu4O[Bo20O32(OH)8]} · 33 H2O, M = 1925.46 g/mol. triclinic, P1̄, a = 1627.4(7), b = 1799.6(9), and c = 1365.2(5) pm; α = 96.37(5), β = 110.93(5), and γ = 111.36(5)°; Z = 2; Dm = 1.96 (flotation) and Dx = 1.91. Mg · m-3; R = 0.155 for 5022 observed reflections, and Na5H{Cu{[B20O32(OH)8]}. 32 H2O, M = 1825.62 g/mol, tetragonal. I4̄, a = 1866 and c = 1042 pm; Z = 2; Dm = 1.63 and Dx = 1.67 Mg · m-3 have been investigated. The structure of the anion icosaboro-μ4-oxo-tetracuprate(II)(6-) contains the largest known isolated borate ion with 20 boron atoms. Each borate ion is a prophyrine-like ring, and encloses four Cu ions in a nearly planar Cu4O cation, thus forming a chelate-like complex. While the anion structure is clear, the positions of the alkalimetal ions and the water molecules are not yet known, although an exact analysis and thermoanalytic determinations confirm the formula.
Über gemischte Bindungen in der IV. Hauptgruppe, II [1]. Hexacyclohexylethan-Analoga Pb2(c-Hex)6, (c-Hex)3Pb–Sn(c-Hex)3 und Sn2(c-Hex)6 / On Mixed Group IVb – Group IVb Bonds, II [1]. Hexacyclohexylethane Analogues Pb2(c-Hex)6, (c-Hex)3Pb–Sn(c-Hex)3, and Sn2(c-Hex)6
Authors: Kleiner Norbert , Drager Martin
Published: March 2015

(c-Hex)3Pb-Sn(c-Hex)3 is synthesized from (c-Hex)3PbLi and (c-Hex)3SnCl at -50 °C in THF. The three title compounds are isomorphous. The compounds have been investigated by mass, NMR and vibrational spectra. Pb2(c-Hex)6: highest fragment Pb2(c-Hex)5
+, 1J(13C-207Pb) 30.2 Hz. 2J(13C-207Pb) 9.1 Hz, δ(207Pb) +81 ppm. (c-Hex)3Pb-Sn(c-Hex)3: highest fragment PbSn(c-Hex)5
+, δ(207Pb) -92 ppm, δ(119Sn) -157 ppm, 1J(207Pb-19Sn) 2217 Hz. Sn2(c-Hex)6: parent peak Sn2(c-Hex)6
+, 1J(13C-119Sn) 113.3 Hz, 2J(13C - 119Sn) 26.4 Hz, δ(119Sn) -71 ppm, 1J(119Sn-119Sn) 1258 Hz, ν(Sn-Sn) 135 cm_1.The crystal structure of Pb2(c-Hex)6 has been deter­mined and refined to R = 0.044. The symmetry of the molecule is C3; distances Pb-Pb 287.6(4), Pb-C 226(2) and 228(3) pm. The cyclohexyl groups are unusual flat and distorted from the normal Cs symmetry; this is in accordance with two sets of 13C NMR signals in benzene-d6.
The Ni(0)–CO2 System: Structure and Reactions of [Ni(PCy3)2(η-CO2)]
Authors: Dohring A. , Jolly P. W. , Kruger C. , Romão M. J.
Published: March 2015

The reactions of a variety of bis(tricyclohexylphosphine)nickel species with CO2 have been studied. The product of the reaction is solvent dependent: in toluene the known complex [NiL2(η2-CO2)] · toluene (L = PCy3) is formed while in ether or pentane a binuclear complex [(NiL2)2(η-CO2)] results through the intermediacy of the solvent free species [NiL2(η2-CO2)] the structure of which has been determined by X-ray crystallography.
Pentacarbonyl-Metallkomplexe von Phosphor(+I)-Chelaten / Pentacarbonyl Metal Complexes of Phosphorus(+I) Chelates
Authors: Lang Heinrich , Zsolnai Laszlo , Huttner Gottfried
Published: March 2015

Phosphorustrihalides react with Na2[M2(CO)10] (M = Cr. Mo, W) to give phosphinidene complexes [(CO)5M]2P-Hal. These species are transformed into phosphorus(+I)-cheiate compounds [XXX]. = tropolonate or 8-hydroxychinolate.
Metallkomplexe mit biologisch wichtigen Liganden, XXXIX [1]. Platin(IV)-Komplexe mit α-Aminosäure-und Peptidestern; 15N-und 195Pt-NMR-Spektren von α-Aminosäuren-Platin-Komplexen / Metal Complexes with Biologically Important Ligands, XXXIX [1]. Platinum(IV) Complexes with α-Amino Acid Esters and Peptide Esters; 13N and 195Pt NMR Spectra of Platinum Complexes with α-Amino Acids
Authors: Bissinger Herbert , Beck Wolfgang
Published: March 2015

The platinum(IV) complexes PtX4L2 (X = Cl, Br; 2 X = oxalate; L = glyOEt, glyglyOEt, gly-cleuOEt; 2 L = metOEt) have been obtained by oxidative addition of halogenes to platinum(II) compounds PtX2L2. A high field shift of δ15N ( ∼ 50 ppm) is observed for the coordinated amino acid ligand of various platinum complexes, compared to the free ligand. Platinum(II) and platinum(IV) can be distinguished by their 195Pt NMR signals.
Notizen: Tetraphenylphosphonium-octabromodiantimonat, (PPh4)2[Sb2Br8]. Synthese und Kristallstruktur / Tetraphenylphosphonium Octabromodiantimonate, (PPh4)2[Sb2Br8]. Synthesis and Crystal Structure
Authors: Mohammed Abdulalah T. , Muller Ulrich
Published: March 2015

(PPh4)2[Sb2Br8] can be prepared from SbBr3 and PPh4Br in CH2Br2 or from Sb2S3, PPh4Br and HBr in 1,2-dichloroethane. Its crystal structure was de­termined with X-ray diffraction data (2764 observed reflexions, R = 0.039). Crystal data: triclinic, space group P1̄, a = 1024.9. b = 1127.1, c = 1282.4 pm, α = 111.80, β = 94.52, γ = 106.92°, Z = 1. The centrosymmetric [Sb2Br8]2- ions consist of two square pyramids sharing a basal edge. The cations are grouped to (PPh4
+)2 pairs similarly as in (PPh4)2[As2Cl8]; although the latter compound has a comparable general crystal packing, it is not isotopic. IR and Raman spectral data are reported.
Die oxidative Addition von NickeI(0)-KompIexen an Kohlenstoff-Kohlenstoff-Bindungen im Cyclobutadien. Zur Frage der Überführbarkeit von Cyclobutadien-Nickel(O)-Komplexen in Nickelaringe / Oxidative Addition of Nickel(O) Complexes to Carbon-Carbon Bonds in Cyclobutadiene. The Question of the Interconvertibility of Cyclobutadiene-nickel(O) Complexes and the Nickelaring Systems
Authors: Eisch John J. , Piotrowski Andrzej M. , Aradi Allen A. , Krüger Carl , Romão Maria J.
Published: March 2015

Bis(triethylphosphine)(η4-tetraphenylcyclobutadiene)nickel (4) was synthesized by the reduction of (η4-tetraphenylcyclobutadiene)nickel(II)bromide (3) with t-butyllithium in the presence of Et3P, and its structure was determined by X-ray crystallography. Furthermore, its reactivity towards CO, CH3CO2H, PhC≡CPh, LiAlH4 and O2 were investigated. 1,1-Bis(triethylphos-phine)-2,3,4,5-tetraphenylnickelole (14) was synthesized from (E,E)-1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene (15) and bis(triethylphosphine)nickel(II)bromide. Since the resulting crystals of the nickelole were not suitable for X-ray structure determination, the compound was characterized by elemental analyses, spectral data and carbonylation to yield tetraphenylcyclo-pentadienone (6).

Analogous reductions of (η4 -tetraphenylcyclobutadiene)nickel(II)bromide (3) in the presence of Ph3P or Ph2PCH2CH2PPh2 , followed by carbonylation, led to 6 in 40% yield, demonstrating that about half of the cyclobutadiene rings in 3 undergo cleavage upon reduction to give the nickelole.

Reactions of the dilithium reagent 15 with NiBr2 complexed with Me2PCH2CH2PMe2 ,Ph3P or Et2PCH2CH2PEt2 , led to the formation of thermolabile nickeloles, as demonstrated by carbonylàtion which yielded 6. Warming of the nickeloles and subsequent treatment with CH3CO2H led to the formation of 1,2,3,4,5,6,7,8-octaphenyl-1,3,5,7-octatetraene (8) and, in one case, octaphenyl-cyclooctatetraene (5).

The relevance of these findings to the mechanism of the Reppe nickel-catalyzed oligomerization of alkynes is discussed.
Synthese neuer 2-Dichlormethylen-thiazolidinon-Derivate / Synthesis of New 2-Dichloromethylene-thiazolidinone Compounds
Authors: Giencke Wolfgang
Published: March 2015

Starting from the 2-trichloromethyl-thiazolidinones 3 and 4 syntheses of the 2-dichloromethy-lene-4-thiazolidinones 5 and the corresponding 1-oxides, 6, 9 and 10 are described. The base used in these elimination reactions is potassium-1,2,4-triazole.
Wolfram-dibromid-trinitrosyl, [WBr2(NO)3]2 Dibromotrinitrosyltungsten, [WBr2(NO)3]2
Authors: Berg Alexander , Dehnicke Kurt
Published: March 2015

Dibromotrinitrosyltungsten, which dimerises via bromo bridges, is prepared by treating tungsten hexabromide with NO in CH2Br2 suspension. It reacts with the Lewis bases acetonitrile, 1,2-dipyridyl, triphenylphosphane, and tetraphenylphosphonium bromide forming the octahedral complexes [WBr,(NO),(CH,CN),]. [WBr2(NO)2(dipy)], [ WBr2(NO)2(PPh3)2], [WBr3(NO)2]2
2⊖, and [WBr4(NO)2]2⊖, respectively. According to the IR spectra all dinitrosyl complexes possess cis-configuration of the nitrosyl groups.
Ein Molekül mit Bismut-Tellur-Bindung: p-Tolyltelluro-di-n-propylbismutan / A Molecule with the Bismut-Tellurium Bond: p-Tolyltellurodi-n-propylbismutane
Authors: Mont Wolf-Walther du , Severengiz Tevfik , Breunig Hans Joachim , Müller Ditmar
Published: March 2015

Tetra-n-propyldibismutane reacts with equimolar amounts of di-p-tolylditelluride to yield p-tolyl-telluro-di-n-propylbismutane in high yield. This tellurobismutane is the first molecule with a Bi-Te bond. It has been characterised by elemental analysis and by NMR and mass spectra.
Proanthocyanidins in the Bark of Saraca asoca Roxb. de Wilde
Authors: Middelkoop T. B. , Labadie R. P.
Published: March 2015

Saraca asoca (Leguminosae), (―)-Epicatechin, Procyanidin (B2), 1 1′-Deoxyprocyanidin B The bark of Saraca asoca is used as a main ingredient in the preparation of Asoka Arishta, a drug indigenous to Sri Lanka. In this paper an investigation on some biologically active constituents of the bark is described.

(―)-Epicatechin and procyanidin B2 were identified and a new compound, named 11′-deoxy-procyanidin B, was found. Its structure was elucidated by means of proton-NMR.
Die Reaktion der unbeständigen Schwefeldiimide S(NR)(NH) (R = H, C(CH3)3, Si(CH3)3) mit den Halbsandwich-Komplexen CpW(CO)3H und Cp*W(CO)3H / The Reaction of the Unstable Sulfur Diimides S(NR)(NH) (R = H, C(CH3)3, Si(CH3)3) with the Halfsandwich Complexes CpW(CO)3H and CpsW(CO)3H
Authors: Herberhold Max , Jellen Wolfgang , Bühlmeyer Wolfgang , Ehrenreich Wolfgang
Published: March 2015

The unstable parent compound of the sulfur diim ides, S(NH)2 (1 ), and the labile monosubstituted sulfur diimides, S(NR)(NH) (R = tert-butyl (2) and trimethylsilyl (3)) react with the halfsandwich com plexes CpW (CO)3H (a) and Cp*W (CO)3H (b) under insertion into the W-H bond. The structures of the addition products (1a -3a, 1b -3b) are interpreted on the basis of a central four-membered metallocycle into which an acyl group and one of the N = S bonds are incorporated. The observation of two species in the 1H and 13C NMR spectra of 1a -3a and 2b, 3b is ascribed to interactions with the solvent.
Schwefelreiche spirozyklische Komplexe: [Zn(S6)2]2–, [Cd(S6)2]2–, [Hg(S6)2]2– und [Hg(S4)2]2– / Sulfur-Rich Spirocyclic Complexes: [Zn(S6)2]2-, [Cd(S6)2]2-, [Hg(S6)2]2- and [Hg(S4)2]2-
Authors: Müller Achim , Schimanski Jürgen , Schimanski Uwe , Bögge Hartmut
Published: March 2015

By reaction of Zn(CH3COO)2·2H2O. Cd(CH3COO)2-2H2O, or Hg(CH3COO)2 with defined alcoholic polysulfide solutions the crystalline compounds (NEt4)2[Hg(S6)2] (1), [(PPh3)2N]2[Cd(S6)2]·CH3CN (2), (PPh4)2[Zn(S6)2] (3) and (PPh4)2[Hg(S4)2] (4) could be obtained. 1-4 were characterised spectroscopically (IR, Raman, UV/VIS) and by X-ray structure analyses.
Die Schichtstruktur des hydratisierten Tetramethylammoniummangan(II)- hexacyanochromats(III), NMe4MnCr(CN)6 · 4H2O / The Layer Structure of the Hydrated Tetramethylammoniummanganese(II)- hexacyanochrom ate(III), NMe4MnCr(CN )6 · 4H2O
Authors: Witzel M. , Babel D.
Published: March 2015

The crystal structure of the orthorhombic compound NMe4MnCr(CN)6-4H:0 has been determined (a = 1496.5, b = 783.8, c = 1727.0 pm, space group Pnma. Z = 4, = 0.06 for 2018 independent reflections). The structure consists of puckered layers formed by Cr(CN)6
3- octahedra (average Cr-C = 207.5 pm, C-N = 114.4 pm), which are two-dimensionally linked via cyano bridges Cr-CN-Mn to trans-dihydrated Mn(H2O)2+ cations (Mn-O = 219.3 pm. Mn-N = 224.4 pm). Between the layers, which are separated by disordered tetramethylammonium ions and additional water molecules, a hydrogen bridge O-H···N is formed by two of the four terminal ligands. The structure found is intermediate between the framework arrangement of CsMnCr(CN)6 and the chain structure of NMe4MnM(CN)8-8H2O. Some further relations are discussed.
Anthracen- und Phenanthren-Cobalt-Verbindungen mit Trimethylphosphan-Liganden / Anthracene and Phenanthrene Cobalt Compounds Containing Trimethylphosphane Ligands
Authors: Klein Hans-Friedrich , Ellrich Klaus , Lamac Susanne , Lull Goetz , Zsolnai Laszlo , Hüttner Gottfried
Published: March 2015

Anthracene and phenanthrene complexes of zerovalent cobalt, Co(Cl4H10)(PMe3)3, are obtained by substitution of olefin in Co(olefin)(PMe3)3 (olefin = propene, cyclopentene). Ethene replaces the η2-bonded aromatic molecules. Substitution labile ligands L′ in hydridocobalt complexes CoH(L′)(PMe3)3 (L′ = N2, C4H8) give way to an anthracene or phenanthrene ligand and can in turn be replaced by carbon monoxide. η4-Coordinated anthracene in Co[Sn(C6H5)3](C14H10)(PMe3)2 is not replaced by CO under normal conditions. In η2-coordinated anthracene the bond between coordinated C-atoms in ring positions 2 and 3 is elongated by 8.9 pm when compared with free anthracene, deviations from planarity of six-membered rings are slight. η4-Coordinated anthracene contains a naphthalin-type planar part and. in the coordinated ring with the longer CC-bonds, shows a folding away from the cobalt atom.
Strukturermittlung der Reduktionsprodukte von Pyridostigmin mit NaBH4 / Determination of the Structure of Products of the Reduction of Pyridostigmine with NaBH4
Authors: Horstmann Volker , Häfelinger Günter
Published: March 2015

The chemical structure of 5 different products of pyridostigmine obtained by reduction with NaBH4 was determined by GC-MS and subsequently confirmed by means of 1H and 13C NMR spectroscopy. Reaction conditions leading almost exclusively to the main product: 3-[(N,N-dimethyl)-carbamoyl]-1-m ethyl-1,2,5,6-tetrahydropyridine (4) have been determined.
Neue Oxide des Formeltyps A2[T3O4]: Rb2Li2SiO4 [1 ] und Rb2Li2GeO4 [2 ] / New Oxides o f the Formula Type A2[T3O4]: Rb2Li2SiO4 [1 ] and Rb2Li2GeO4 [2 ]
Authors: Hofmann Ralf , Nowitzki Bernd , Hoppe Rudolf
Published: March 2015

Rb2Li2Si04 and Rb2Li2Ge04 were prepared from the binary oxides in closed Ni-tubes at 800 and 850 °C, respectively.

Crystal structures of the isotypic compounds were determined from four-circle diffractometer data (2018 and 1509 Io(hkl), R = 8.37%, Rw = 6.39% and R = Rw = 13.68%). They crystallize triclinically, P1̄, a = 897.92(11), b = 564.73(5), c = 546.99(6) pm, α = 93.95(10), β = 111.24(9), γ = 93.75(10)° (Rb2Li2SiO4) and a = 905.4(9), b = 575.4(7), c = 560.6(7) pm, α = 94.67(9), β = 110.82(10), γ = 93.60(9)° (Rb2Li2GeO4) (Guinier-Simon-data). Z = 2. Effective Coordination Number (ECoN) and Madelung Part of Lattice Energy (MAPLE) values were calculated. The structure is described using Schlegel-diagrams.
Radikalionen, 69 [1, 2] Die elektrochemische Reduktion aromatischer Nitro-Verbindungen in aprotischer Lösung / Radical Ions, 69 [1, 2] The Electrochemical Reduction of Aromatic Nitro Compounds in Aprotic Solution
Authors: Bock Hans , Lechner-Knoblauch Ulrike
Published: March 2015

The reduction potentials of 40 aromatic nitro compounds Rπ(NO2)n with Rπ = benzene, naphthalene, anthracene, fluorene and carbazole and n = 1 to 4 nitro groups are determined by cyclic voltammetry in DMF under aprotic conditions. The perturbation by the strongly electron accepting substituents can be rationalized via correlation with HMO eigenvalues. Based on reversibility criteria, the electrochemical behaviour is discussed and the compounds are classified with respect to reversible or irreversible one-electron transfer as well as up to 4 (quasi)-reversible reduction steps. The CV data measured can be used to predict redox reactions of aromatic nitro compounds in inert solvents.
Synthese gemischtsubstituierter Triorganobismutane / Synthesis of Mixed Substituted Triorganobismuthanes
Authors: Wieber Markus , Sauer Ingbert
Published: March 2015

Sodium dimethylbismuthide, generated from dimethylbismuth bromide and sodium in liquid ammonia, was treated with alkyl halides to produce dimethylalkylbismuthanes, Me2Bi(alk) (alk = C2H5, n-C3H7, n-C4H9, C3H5, i-C3H7) as thermolabile liquids in yields ranging from 70 to 90%. With methylene chloride bis(dimethylbismutho)methane, (Me2Bi)2CH2, was obtained. Aryldimethylbismuthanes, (aryl)BiMe2, were prepared by treating dimethylbismuth bromide in THF with elemental lithium (-78 °C) and subsequent reaction with aryl halides (aryl = 4-C6H4CH3, 4-C6H4OCH3, 2,4,6-C6H2(CH3)3). At 90 °C in an N2-stream, the thermolabile compounds react quantitatively to form diarylmethylbismuthanes, (aryl)2BiMe and Me3Bi.
Über Zinn-haltige Heterocyclen, IX [1] Methylphenylstannocane, transannulare Sn···O und Sn···S-Wechselwirkungen an einem asymmetrisch substituierten Sn-Atom / On Heterocyclic Systems Containing Tin, IX [1] Methylphenylstannocanes, Transannular Interactions Sn···O and Sn···S at Asymmetrically Substituted Tin
Authors: Dräger Martin
Published: March 2015

Methylphenyl oxadithia and trithiastannocane have been synthesized from MePhSnCl2 and the respective disodium dithiolate. The crystal structure of the oxadithiastannocane has been deter­mined (R = 0.0535). The coordination geometry is midway between a tetrahedron and a trigonal bipyramid (equatorial Sn−S 241.4(3) and 240.5(3). Sn−Me 212.7(8) pm; axial Sn−Ph 215.0(6). Sn···O 267.6(6) pm). By using the bond angles this coordination case is inserted in a series of analogous compounds and compared with vibrational data.
New Dehydrothymol Derivative from Iphiona mucronata
Authors: Metwally Mohamed
Published: March 2015

A reinvestigation of Iphiona mucronata gave in addition to the known compound a new dehydrothymol derivative. Its structure was determined by spectroscopic methods.
PNP-Perthionitrit und PNP-Monothionitrit / PNP-Perthionitrite and PNP-M onothionitrite
Authors: Seel F. , Kuhn R. , Simon G. , Wagner M.
Published: March 2015

As a major product from the reaction of PNP-nitrite [P = P(C6H5)3] with elementary sulfur or a PNP-polysulfide (PNP)2S12 in acetone under anaerobic conditions PNP-perthionitrite (PNPnitrosodisulfide) PNP-SSNO has been isolated. VIS/UV-spectra point to a thionitrate or perthionitrate as a precursor.

The structures of PNP-SSNO and of the product obtained on treating the perthionitrite with triphenylphosphane in acetonitrile, PNP -SNO (PNP-monothionitrite, PNP-nitrososulfide), have been elucidated through X-ray diffraction and independently from new chemical and NMRspectrometric arguments. PNP-SSN O crystallizes in the orthorhombic space group P ben with a = 11.843(3), b = 16.647(5), c = 15.556(4) Å , PNP -SNO in the triclinic group P1̄ with a = 10.525(3), b = 17.196(5), c = 9.451(3) Å , a = 95.22(3), β = 92.32(3), γ = 91.65(3)°.
Über Erdalkalimetallverbindungen des 1,1-Dicyanoethylen-2,2-dithiolats, II+ Die Kristallstruktur von BaS2C4N2 • 3 H2O / On Alkaline-Earth Metal Compounds of 1,1-D icyanoethylene-2,2-dithiolate, II+ Crystal Structure of BaS2C4N2 • 3 H2O
Authors: Hummel Hans-U. , Wolf C.
Published: March 2015

By reaction of CS2 with maleonitrile in the presence of sodium-ethanolate in ethanol Na2S2C4N2 is obtained. It reacts with Ba(NCS)2 · 3 H2O in a metathesis reaction to give BaS2C4N2 ·3 H2O. The space group of the barium salt is C 2/c with Z = 8. The structure consists of Ba2+ and [S2C -C(CN)2]2- ions, and crystal water. Barium has a distorted tricapped trigonal prismatic coordination: four O, three N and two S atoms. There are considerable deviations from planarity for the [S2C4N2]2- anion due to packing effects
Zur Hochdruckpolymorphie der Seltenerdsulfidfluoride LnSF (Ln: Er, Yb, Lu) / High Pressure Polymorphism of Rare Earth Sulfidefluorides LnSF (Ln: E r, Yb, Lu)
Authors: Beck H. P. , Strobel C.
Published: March 2015

The sulfidefluorides LnSF with Ln = Er, Yb, Lu undergo a high pressure transformation from the β-YSF- to a PbFCl-type structure. The structures involved and a proposed reaction mechanism are explained in terms of a topological description
Isomere ω-Carboxyalkylpyridone aus 5,6,7,8-Tetrahydro-1,3-dimethyI- 8-oxochinolinium-iodid / Isomeric ω-Carboxyalkylpyridones from 5,6,7,8-Tetrahydro-1,3-dimethyl- 8-oxochinolinium-iodide
Authors: Lippe Gotelind von der , Weber Horst
Published: March 2015

Alkaline hexacyanoferrate(III) oxidation (Decker oxidation) of the title compound 9 yields the isomeric pyridones 10 and 11 in nearly equal amounts whereas the pyridinium salt 12 gives only the carboxylic acid 10 under this conditions. From this result it is concluded that 9 is not an indermediate during the oxidation of 12. Spectroscopic data of 10 and 11 are compared for structural determination. A HPLC-method is described concerning quantitative analysis of a mixture of 10 and 11 via the corresponding 4-bromophenacylester derivatives
103Rh-NMR bei 9,4 T - Verbesserter Nachweis infolge verkürzter Relaxationszeiten und selektivem Polarisationstransfer / 103Rh NMR at 9.4 T - Improved Signal Detection due to Shortened Relaxation Times and Selective Polarisation Transfer
Authors: Benn Reinhard , Brenneke Herbert , Reinhardt Rolf-Dieter
Published: March 2015

At 9.4 T the I03Rh relaxation times (T ,) of unsym metrical organorhodium com pounds of the type LR h(7r-ligand) 2 are in the order of seconds, and relaxation is dominated by the Chemical Shift Anisotropy mechanism. In symmetrical complexes like (acac)3Rh (7), T, of 103Rh is considerably longer and dominated by the Spin Rotation mechanism. Through this effect, together with selective polarisation transfer via the Rh olefin-proton spin-spin couplings at high magnetic fields, a significantly improved detection of the insensitive Rh nucleus results
Antipsychotic Medication Prescribing in Children Enrolled in Medicaid
Authors: Rettew David C. , Greenblatt Jeanne , Kamon Jody , Neal Diane , Harder Valerie , Wasserman Richard , Berry Patricia , MacLean Charles D. , Hogue Nancy , McMains William
Published: March 2015

BACKGROUND:

Although the increase in treatment of children and adolescents with antipsychotic medications has been well documented, much less is known about the factors related to the use of these agents and how closely the treatment follows best practice recommendations.

METHODS:

Prescribers of each antipsychotic medication prescription issued for a Medicaid-insured child in Vermont aged <18 years were sent a prior authorization survey that assessed several domains including the clinical indication, other treatments, metabolic monitoring, prescriber specialty, and prescription origin. These variables were combined to categorize prescriptions as following indications approved by the US Food and Drug Administration (FDA) and best practice guidelines.

RESULTS:

The response rate of the survey was 80%, with 677 surveys from 147 prescribers available for analysis; more than one-half of the respondents were primary care clinicians. Overall, the clinical indication for an antipsychotic prescription followed best practice guidelines 91.7% of the time, with overall best practice guidelines followed at a rate of 50.1%. An FDA indication was followed in 27.2% of cases. Psychiatrists were significantly more likely to follow best practice guidelines than nonpsychiatrists. Antipsychotic medications were typically used only after other pharmacologic and nonpharmacologic treatments were ineffective, although previous treatment with cognitive-behavioral therapy was uncommon (15.5%). Metabolic monitoring that included serial laboratory tests was reported in 57.2% of cases.

CONCLUSIONS:

Current prescribing patterns of antipsychotic medications for children and adolescents follow best practice guidelines approximately one-half of the time, with nonadherence often related to lack of metabolic monitoring.
Pneumonia in Childhood and Impaired Lung Function in Adults: A Longitudinal Study
Authors: Chan Johnny Y.C. , Stern Debra A. , Guerra Stefano , Wright Anne L. , Morgan Wayne J. , Martinez Fernando D.
Published: March 2015

BACKGROUND:

Diminished lung function and increased prevalence of asthma have been reported in children with a history of early lower respiratory illnesses (LRIs), including pneumonia. Whether these associations persist up to adulthood has not been established.

METHODS:

As part of the prospective Tucson Children's Respiratory Study, LRIs during the first 3 years of life were ascertained by pediatricians. Spirometry was performed at ages 11, 16, 22, and 26 years. The occurrence of asthma/wheeze during the previous year was ascertained at ages 11, 13, 16, 18, 22, 24, 26, and 29 years. Longitudinal random effects models and generalized estimating equations were used to assess the relation of LRIs to lung function and asthma.

RESULTS:

Compared with participants without early-life LRIs, those with pneumonia had the most severe subsequent lung function impairment, with mean ± SE deficits of −3.9% ± 0.9% (P < .001) and −2.5% ± 0.8% (P = .001) for pre- and post-bronchodilator FEV1:FVC ratio from age 11 to 26 years, respectively. Pneumonia was associated with increased risk for asthma (odds ratio [OR]: 1.95; 95% confidence interval [CI]: 1.11–3.44) and wheeze (OR: 1.94; 95% CI: 1.28–2.95) over the same age range. Early non-pneumonia LRIs were associated with mildly impaired pre-bronchodilator FEV1 (−62.8 ± 27.9mL, P = .024) and FEV1:FVC ratio (−1.1 ± 0.5%, P = .018), and wheeze (OR: 1.37; 95% CI: 1.09–1.72).

CONCLUSIONS:

Early pneumonia is associated with asthma and impaired airway function, which is partially reversible with bronchodilators and persists into adulthood. Early pneumonia may be a major risk factor for adult chronic obstructive pulmonary disease.
Physician Response to Parental Requests to Spread Out the Recommended Vaccine Schedule
Authors: Kempe Allison , O’Leary Sean T. , Kennedy Allison , Crane Lori A. , Allison Mandy A. , Beaty Brenda L. , Hurley Laura P. , Brtnikova Michaela , Jimenez-Zambrano Andrea , Stokley Shannon
Published: March 2015

OBJECTIVES:

To assess among US physicians (1) frequency of requests to spread out recommended vaccination schedule for children <2 years, (2) attitudes regarding such requests, and (3) strategies used and perceived effectiveness in response to such requests.

METHODS:

An e-mail and mail survey of a nationally representative sample of pediatricians and family physicians from June 2012 through October 2012.

RESULTS:

The response rate was 66% (534 of 815). In a typical month, 93% reported some parents of children <2 years requested to spread out vaccines; 21% reported ≥10% of parents made this request. Most respondents thought these parents were putting their children at risk for disease (87%) and that it was more painful for children (84%), but if they agreed to requests, it would build trust with families (82%); further, they believed that if they did not agree, families might leave their practice (80%). Forty percent reported this issue had decreased their job satisfaction. Most agreed to spread out vaccines when requested, either often/always (37%) or sometimes (37%); 2% would often/always, 4% would sometimes, and 12% would rarely dismiss families from their practice if they wanted to spread out the primary series. Physicians reported using a variety of strategies in response to requests but did not think they were effective.

CONCLUSIONS:

Virtually all providers encounter requests to spread out vaccines in a typical month and, despite concerns, most are agreeing to do so. Providers are using many strategies in response but think few are effective. Evidence-based interventions to increase timely immunization are needed to guide primary care and public health practice.