bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stabile Tellur‐Ylide: Darstellung und Reaktivität von Diorganyltelluronium‐4,5‐dicyanimidazol‐2‐yliden
Authors: Tappeiner Günther , Bildstein Benno , Sladky Fritz 
Published: July 2007

Stable Tellurium Ylides: Synthesis and Reactivity of Diorganyltelluronium 4,5‐Dicyanoimidazol‐2‐ylidesDiorganyl tellurides R2Te (RMe, Me3SiCH2, Ph) react with 2‐diazo‐4,5‐dicyano‐2H‐imidazole (1) at – 30°C to form the title compounds 2 – 4. The ylides 3 and 4 are thermally stable up to their melting points of 159 and 243°C, resp., whereas 2 undergoes a modified Stevens rearrangement at 190°C with formation of a 2‐(methyltelluro)imidazole (10). The reactivity of 2 – 4 is determined by an extreme charge separation between the onium centre and the ylide entity. No Wittig reactivity is observed, alkylation occurs at the imidazole nitrogen and carbanions lead to tetraorganyl tellurium compounds with limited stability.
d8‐Eisennitrosylhydride
Authors: Jänicke Monika , Hund Hans‐Ulrich , Berke Heinz 
Published: July 2007

d8 Iron Nitrosylhydride ComplexesThe nitrogen complex [(OC)2(Et3P)2Fe]2N2 (1) reacts with carboxylic acids to form the complexes (OC)2(Et3P)2Fe(H)OC(O)R [R=4‐methoxyphenyl, 2a; R=2,4‐dimethoxyphenyl, 2b; R=2,4,6‐trimethoxyphenyl, 2c; R – Ph, 2d; R – CF3, 2e]. Treatment of 2 with N‐methyl‐N‐nitroso‐p‐tolylsulfonamide produces the nitrosylcarboxylato complexes (OC)(ON)‐(Et3P)2FeOC(O)R (3a – d) in addition to the side product Fe(NO)2(PEt3)2 (4) except for 2e which forms 4 exclusively. Reaction of 3 with LiAlH4 yields the hydridonitrosyliron complex (OC)(ON)(Et3P)2FeH (5a). A different synthetic route to the phosphorus donor‐substituted iron hydride complexes involves starting material (OC)2(L)2FeCl2 [LPEt3, 6a; L – PMe3, 6b; LP(OiPr)3, 6c]. Compounds 6 react with tBuLi and NOBF4 to form (OC)(ON)L2FeCl (7). Subsequent treatment with NaBH4 gives (OC)(ON)(L)2FeH [LPEt3, 5a; LPMe3, 5b; LP(OiPr)3, 5c]. The structures of 5b and 7a are determined by X‐ray crystallography.
Übergangsmetall‐substituierte Diphosphene, XXIII. Studien zur Synthese und Reaktivität von Dihalogenphosphido‐Komplexen des Eisens und Rutheniums
Authors: Weber Lothar , Sonnenberg Uwe 
Published: July 2007

Transition‐Metal‐Substituted Diphosphenes, XXIII. ‐Studies on the Synthesis and Reactivity of Dihalophosphido Complexes of Iron and Ruthenium(η5‐C5Me5)(CO)2FeP(SiMe3)2 (1a) reacts with two equivalents of C2Cl6 to give the dichlorophosphido complex (η5‐C5Me5)‐(CO)2FePCl2 (2a). The latter is easily converted into (η5‐C5Me5)(CO)2FeP(E)Cl2 (3; ES; 4: ESe) by treatment with the respective chalcogen. The reaction of 1a with 2a leads to a mixture of the cyclotriphosphane [(η5‐C5Me5)‐(CO)2FeP]3 (8a) and the bicyclo[1.1.0]tetraphosphane [(η5‐C5Me5)(CO)2FeP)2P2(10). The same result is obtained when 1a is treated with only one equivalent of C2Cl6. In addition the dihalophosphido complexes (η5‐C5Me5)(CO)2RuPCl2 (2c), (η5‐C5H5)(CO)(PPh3)FePCl2 (2b), (η5‐C5Me5)(CO)2FePBr2 (2d), and (η5‐C5Me5)(CO)2FePI2 (2e), and the cyclotriphosphane [(η5‐C5Me5)(CO)2RuP]3 are synthesized.
Synthese und Struktur von Ph3PNRe(NC6H3iPr2;‐2,6)3 ‐eine Aza‐Rhenium(VII)‐Verbindung
Authors: Roesky Herbert W. , Hesse Detlev , Noltemeyer Mathias , Sheldrick George M. 
Published: July 2007

Synthesis and Structure of Ph3PNRe(NC6H3iPr2;‐2,6)3 ‐ An Aza‐Rhenium (VII) Compound.Ph3PNReO3 (1) reacts with three equivalents of 2,6‐diisopropylphenyl isocyanate with evolution of CO2 to give the title compound 2. The X‐ray single crystal structure of 2 exhibits a rhenium atom tetrahedrally coordinated to four nitrogen atoms (space group P 3).
Decacarbonyl(μ3;‐η2‐‖‐1,4‐dimethoxy‐2‐butyne)triiron, an Iron Cluster with Unusual Structure
Authors: Lentz Dieter , Reuter Marion 
Published: July 2007

AbstractReaction of undecacarbonyl(acetonitrile)triiron (1) with 1,4‐dimethoxy‐2‐butyne (2) yields the alkyne complexes decacarbonyl(μ3;‐η2‐Verbar‐1,4‐dimethoxy‐2‐butyne)triiron (3) and nonacarbonyl(μ3;‐η2;‐⊥‐1,4‐dimethoxy‐3‐butyne)triiron (4). The crystal structure determination of 2 shows that the alkyne ligand is coordinated strictly parallel to one iron‐iron edge.
Über die optische Drehung von Quaterphenyl‐Derivaten
Authors: Fischer Erika , Hess Heinrich , Lorenz Thomas , Musso Hans , Ro ßnagel Ingrid 
Published: July 2007

Optical Rotation of Quaterphenyl DerivativesQuatermesityl (2) has been resolved by chromatography into pure enantiomers; (S)‐(+)‐2 shows [α]D=+ 108 as expected. (S)‐(+)‐3,3′‐Diphenylbimesityl (9) has been prepared enantiospecifically and shows [α]D=+ 106. Chromatographic resolution of 9 as well as of quinquemesityl (15) succeeded, too. The optical activity of chiral polyphenyl derivatives is discussed. The interplanar angles of the quaterphenyl derivatives 2, 9, and 14 are presented.
Small and Medium Rings, 75. Syntheses, Photoelectron Spectra, and Photoreactivity of Polycyclic 1,5‐Diketones: Transannular Interaction in the Cyclooctane‐1,5‐dione Fragment
Authors: Albert Bernhard , Els ässer Dominik , Heckel Dieter , Kopmeier Siglinde , Mayer Bernhard , Martin Hans‐Dieter , Yeh Show‐Kei , Chow Tahsin J. , Wu Tung‐Kung 
Published: July 2007

AbstractFive polycyclic 1,5‐diketones 1 – 4 and 6 are synthesized and studied by means of He(Iα) PE spectroscopy. Comparison of the spectra indicates significant differences in Orbital Interaction Through Bond, which is explained by computational methods, especially by analyses of the precanonical MOs. The lone pair splitting observed in diketone 1, ΔI(n)=0.75 eV, seems to be the largest one ever found in a 1,5‐diketone, obviously due to a favourable zigzag topology of the σ frame. In addition, coupling reactions and photoreactivity are studied in compound 6, which seemed to be well suited for Orbital Interaction Through Space. The crystal structure of 6 and its photoproduct 21 is solved by X‐ray crystallography.
Chromophore Systeme, 1. Konformation und Lichtabsorption von Hexa‐1,5‐dien‐3,4‐dion (Divinylglyoxal)
Authors: Bühl Michael , Kramme Roland , Martin Hans‐Dieter , Mayer Bernhard , Nowack Gerhard 
Published: July 2007

Chromophoric Systems, 1. — Conformation and Absorption of Light in Hexa‐1,5‐diene‐3,4‐dione (Divinylglyoxal)Divinylglyoxal (1) is investigated by several spectroscopic and theoretical methods in order to set up a correlation between the CO/CO dihedral angle and the transition energies in unsaturated α‐diketones. According to the experimental (UV, IR, 13C‐NMR, PE spectroscopy and dipole moment) and theoretical (ab initio and molecular mechanics) results, 1 exists predominantly as a C2h conformer (Θco/co=180°, ΘVinyl/co=0°). The dependence of transition energies on CO/CO dihedral angles is similar in shape to that for saturated α‐diketones, but is significantly shifted to lower transition energies. 13C chemical shifts respond sensitively to CO/CO dihedral angles, and the ab initio calculated curve is supported by a few experimental results.
Monomere und überbrückte oligomere (Tetrasulfophthalocyaninato)eisen(II)‐Komplexe mit Isocyaniden und N‐Donoren als axialen Liganden
Authors: Hirsch Andreas , Hanack Michael 
Published: July 2007

Monomeric and Bridged Oligomeric (Tetrasulfophthalocyaninato)iron(II) Complexes with Isocyanides and N‐Donors as Axial Ligands(Tetrasulfophthalocyaninato)iron(II) (TsPcFe) (1) is treated with the isocyanides tert‐butyl isocyanide (tBuNC), 1,4‐diisocyanobenzene (dib), 2,3,5,6‐tetramethyl‐1,4‐diisocyanobenzene (me4dib), and 4‐isocyano‐3,5‐dimethylpyridine (me2pyNC), and also with pyrazine (pyz) leading to bisaxially coordinated monomers TsPcFe(L)2 (L=tBuNC, dib, me4dib) and the bridged oligomers [TsPcFe(L)]n (Ldib, me4dib, me2pyNC, and pyz). All these complexes are soluble in methanol or water. The spectroscopic properties of the complexes are described, and the average chain lengths of the bridged oligomers are determined by 1H‐NMR spectroscopy. The bridged stacked systems exhibit semiconducting properties with and without iodine doping.
Großflächige Makrocyclen aus p‐Quaterphenyl‐Bauteilen
Authors: Vögtle Fritz , Kadei Klaus 
Published: July 2007

Flat Macrocycles Based on p‐Quaterphenyl Units[1.1](3,3′″)‐p‐Quaterphenylophanes 1 – 3 are synthesized via 6 – 12 starting with biphenyl derivative 5. The properties of 1 – 3 (UV, NMR) and their charge‐transfer complexation are compared to p‐quaterphenyl. 1 – 3 are high‐melting, colorless solids, which are sparingly soluble in common organic solvents. They contain two “isolated” p‐quaterphenyl units. Similar to p‐quaterphenyl, 2, 2a and 3 form greenish‐blue chargetransfer complexes with tetracyanoethene (TCNE) in CH2Cl2.
übergangsmetall‐substituierte Acylphosphane und Phosphaalkene, XV. Zur Umsetzung des Phosphaallylkomplexes (η5‐C5Me5)(CO)Fe‐{η3‐P[CH(SiMe3)2](CHCO)} mit Chalcogenen und Fe2(CO)9
Authors: Weber Lothar , Nolte Uwe , Stammler Hans‐Georg , Neumann Beate 
Published: July 2007

Transition‐Metal‐Substituted Acylphosphanes and Phosphaalkenes, XV. – Reaction of the Phosphaallyl Complex (η5‐C5Me5)(CO)Fe{η3‐P[CH(SiMe33)2](CHCO}} with Chalcogenes as well as with Fe2(CO)9The (η3‐phoshaalyl)iron complex (η5‐C5Me5)(CO)Fe{η3‐P(CH(SiMe3)2](CHCO)} (1) is oxidized by sulfur and selenium to afford the methylenethioxo‐ and methyleneselenoxophosphorane complexes 4 and 5 with an anti‐configuration of the CH(SiMe3)2 substituent relative to iron. The chalcogene atoms are attached to the phosphorus atom of the ligand and do not participate in the bonding to the metal Equivalent amounts of 1 and Fe2(CO)9 lead to the phosphaalkenyl complex 6 with an Fe – C σ bond. On the other hand, a large excess of Fe2(CO)9 converts 1 as well as 6 into the cluster compound 7 featuring the bridging 1‐oxa‐4‐phosphabutadiene ligand (η5‐C2Me5)(CO)2Fe—C(O)—CHP—CH(SiMe3)2. Constitution and configuration of all compounds have been elucidated by spectroscopic methods (IR, 1H, 13C, 31P NMR, and MS). In addition complexes 5 and 7 have been characterized by single crystal X‐ray diffraction analyses.
Heterocyclen als Liganden, XI. Octamethyl‐1,1′‐diazaferrocen als bifunktionelle Stickstoff‐Base
Authors: Kuhn Norbert , Kuhn Annette , Lampe Eva‐Maria 
Published: July 2007

Heterocycles as Ligands, XI. – Octamethyl‐1,1′‐diazaferrocene as a Bifunctional Nitrogen Base(C4Me4N)2 Fe·2 HNC4Me4 (3) reacts with Brønstedt and Lewis acids to give the adducts [(C4Me4N·E)2Fe]n+ [4 – 6, 11 – 13; n=2, EH, CH3, CH3C(O); n=O, EBH3, BF3, Fe(CO)4]. The stepwise substitution of the tetramethylpyrrole molecules in 3 leads to the complexes [(C4Me4N·E)(C4Me4N·E')Fe]n+ [16, 17, 19; n – O, EC4Me4NH, E'=Fe(CO)4; n=1, EBH3, E'=H; n=2, EH, E'=CH3]. Similarly, the complexes [{(C4Me4N)C(O)CH2CH2C(O)(NC4me4}Fe]Cl2 (9) and [Ag2{μMe4N)2Fe}2Fe}2](BF4)2·2 MeOH (15) are obtained. Reaction of [(C4Me4NH)2Fe](BF4)2 (4) with nBuLi gives the protonated diazaferrocene [(C4Me4NH)(C4Me4N)Fe]BF4 (18) from which the dimeric iron diamide {(C4Me4N)2Fe}2 (20) is obtained on further deprotonation.
Metallkomplexe mit biologisch wichtigen Liganden, LVIII. C‐Allylglycin‐ und C‐Vinylglycin‐Komplexe von Palladium(II), Platin(II), Rhodium(III), Iridium(III) und deren Reaktionen mit Nucleophilen
Authors: Zahn Ingo , Polborn Kurt , Wagner Barbara , Beck Wolfgang 
Published: July 2007

Metal Complexes of Biologically Important Ligands, LVIII. – C‐Allylglycine and C‐Vinylglycine Complexes of Palladium(II), Platinum(II), Rhodium(III), Iridium(III) and Reactions with NucleophilesThe synthesis of the complexes (R13P)(Cl2Pt(C‐allylglycine ester) (1), (2) and of (η5‐C5Me5)Ir(C‐allylglycinate) (6) with tridentate O,N,η2;‐CC allylglycinate as ligand is described. Addition of enolates (Nu−) to the coordinated CC bond of 2 gives the γ‐C‐metallated α‐amino acid ester complexes (3). In most cases the platination occurs stereoselectively to yield the five‐membered metallacycle with the substitutents CH2Nu and CO2R2 in trans position. From 3d the new α‐amino acid H2NCH(CO2Me)‐(CH2)3C(Ph)(CO2Et)21 (4) is cleaved. The structures of 3c and 6 have been determined by X‐ray diffraction. C‐Vinylglycinate can be stabilized at the metal atom in the complexes (10) (MRh, Ir).
Synthese stabiler Alkantellurenyl‐pseudohalogenide und ‐pseudochalkogenide: (Me3Si)3CTeX (X=–CN, – SCN, – SeCN, – NCO, – N3) und (Me3Si)3CTe–Y–TeC(SiMe3)3 (Y=– NCN–, – NSN–)
Authors: Fimml Walter , Sladky Fritz 
Published: July 2007

Synthesis of Stable Alkanetellurenyl Pseudohalides and Pseudochalcogenides: (Me3Si)3CTeX (X=– CN, – SCN, – SeCN, – NCO, – N3) and (Me3Si)3CTe–Y – TeC(SiMe3)3 (Y=– NCN–, – NSN–)The first stable and isolable alkanetellurenyl pseudohalides and pseudochalcogenides, tris(trimethylsilyl)methanetellurenyl cyanide, thiocyanate, selenocyanate, isocyanate, azide (2–6) as well as bis[tris(trimethylsilyl)methyltelluro]carbodiimide and ‐sulfur diimide (7, 8) are obtained in high yields by the reaction of tris(trimethylsilyl)methanetellurenyl iodide (1) with the silver or potassium salts of the respective pseudohalides or pseudochalcogenides. 5–8 are also the first alkyltellurium(II) compounds with Te–N bonding. All compounds have been characterized by 1H‐, 13C‐, 125Te‐NMR, mass, and IR spectroscopy.
Übergangsmetallkomplexe von Diazenen, XXVII. Eisencarbonyl‐induzierte o‐Semidin‐Umlagerung von 1‐Alkyl‐2‐aryldiazenen
Authors: Kisch Horst , Rei ßer Peter , Knoch Falk 
Published: July 2007

Iron Carbonyl Induced o‐Semidine Rearrangement of 1‐Alkyl‐2‐aryldiazenesIrradiation of pentacarbonyl iron in the presence of Me3C – NN – Ar (Arphenyl, p‐tolyl, p‐CH3OC6H4) produces in the first step ortho‐metallated complexes of the type Me3C – N – N(H)RC6H3Fe(CO)3Fe(CO)3 (2a–c, RH, Me, MeO). In a thermal consecutive step these intermediates undergo an o‐semidine rearrangement to Me3C – NFe(CO)3 – Fe(CO)3N(H)RC6H3 (1a–c). The structure of 1a has been elucidated by X‐ray structure analysis. Dynamic 13C‐NMR spectra indicate restricted rotation of the Me3C group and hindered carbonyl scrambling for the latter and former complexes, respectively.
Beiträge zur Chemie des Phosphors, 211. Pentaisopropyltetracycloundecaphosphan, P11iPr5 – Darstellung und kernresonanzspektroskopische Strukturbestimmung
Authors: Baudler Marianne , Jachow Harald , Floruss Andrea , Hasenbach Jürgen 
Published: July 2007

Contributions to the Chemistry of Phosphorus, 211. – Pentaisopropyltetracycloundecaphosphane, P11iPr5 – Preparation and Structure Determination by Nuclear Magnetic ResonancePentaisopropyltetracycloundecaphosphane (1) has been obtained by reaction of iPrPCl2 with P4 and magnesium and subsequent thermolysis of the crude reaction product, and has been isolated in 91% purity. According to NMR‐spectroscopic investigations, 1 has a constitution analogous to that of the hydrocarbon 2,8‐ethanonoradamantane, thus being 3,4,7,9,11‐pentaisopropyltetracyclo[6.2.1.02,6.05,10]undecaphosphane Compound 1 is formed as a mixture of two configurational isomers 1a and 1b, which differ from each other in their spatial arrangements of the isopropyl groups at P3 and P4.
Lösliche Lanthanid‐alkoxide mit niedrigen Koordinationszahlen am Metall‐Atom
Authors: Wedler Michael , Gilje John W. , Pieper Ursula , Stalke Dietmar , Noltemeyer Mathias , Edelmann Frank T. 
Published: July 2007

Soluble Lanthanide Alkoxides with Low Coordination Numbers at the Metal AtomNd[N(SiMe3)2]3(thf)2 (1) reacts with tBu3COH (2) to give the monomeric lanthanide alkoxide (tritox)3Nd(thf) (3). The chloro‐bridged dimer [(tritox)2Nd(μ‐Cl)thf]2 (6) is obtained by treatment of NdCl3(thf)2 (4) with LiOCtBu3 (5). The structure of 6 has been determined by X‐ray crystallography.
Organophosphorverbindungen, 48. 1‐Halogen‐1H‐phosphirene aus Phosphaalkinen und Halogencarbenen
Authors: Wagner Oliver , Ehle Michael , Birkel Manfred , Hoffmann Jürgen , Regitz Manfred 
Published: July 2007

Organophosphorus Compounds, 48. – 1‐Halogen‐1H‐phosphirenes from Phosphaalkynes and ChlorocarbenesHalogen‐substituted carbenes (7a – i), generated by thermolysis of diazirines (11a–i), add onto phosphaalkynes (8a–c) to form the title compounds (10a–1). Initially formed 2H‐phosphirenes (9) could not be detected as their subsequent conversion to the 1H‐isomers 10 by a 1,3‐halogen shift is very fast. Hydrolysis of 10c,e,g–i and k yields vinylphosphonous acids (17a – e). 1‐Chloro‐1H‐phosphirenes are transformed by nucleophilic substitution into fluoro (10a,c,e → 19a–c), bromo (10c,e → 20a,b), and iodo analogs (10c,e → 21a,b) with the help of silver tetrafluoroborate, trimethylsilyl bromide, and trimethylsilyl iodide, respectively. A crystal structure analysis of 10c is reported.
Intra‐ und extraannular funktionalisierte [2.2.2]Phane mit Dreifachbindung: Synthese und Eigenschaften
Authors: Knops Peter , Vögtle Fritz 
Published: July 2007

Intra‐ and Extraannularly Functionalized [2.2.2]Phanes: Syntheses and PropertiesThe severely strained new cyclophanes 7b–f, consisting of bridged tolane subunits and bearing intraannular substituents R, were prepared mainly to study steric interactions of R with the “π cloud” of the triple bond. These compounds exist in a rigid twisted conformation, whereas the unsubstituted reference compound 7a and the extraannularly functionalized azo compound 9 show C2 symmetry. 9 forms a 1 : 1 clathrate with toluene.
4‐Amino‐3‐pyridiniochinolin‐2(1H)‐on‐chloride und 3,4‐Diaminochinolin‐2(1H)‐one
Authors: Gewald Karl , Sch äfer Harry , Bellmann Peter , Müller Heike 
Published: July 2007

4‐Amino‐3‐pyridinioquinolin‐2(1H)‐one Chlorides and 3,4‐Diaminoquinolin‐2(1H)‐onesN;‐(Chloroacetyl)anthranilonitriles 1 react with the pyridines 2 to form the 4‐amino‐3‐pyridinioquinolin‐2(1H)‐one chlorides 4, which are converted into the pyrido[1',2′ : 1,2]imidazo[5,4‐c]‐ quinolin‐6(5H)‐ones 6 in the presence of sodium hydroxide or by cyclooxidation with bromine. Treatment of 4 with hydrazine hydrate yields the 3,4‐diaminoquinolin‐2(1H)‐ones 9. Analogously to other o‐diamines the substituted imidazo [4,5‐c]‐ quinolinones 12, the pyrazino[2,3‐c]quinolinones 13, 14, the 1,2,5‐thiadiazolo[3,4‐c]quinolin‐4‐one 15a and the 1,2,5‐selena‐diazolo[3,4‐c]quinolin‐4‐one 15b are obtainable from 9a. With chloroacetyl chloride 9a provides the oxazino[2,3‐b]quinolin‐2‐one 11.
An easy access to (S)‐ and (R)‐hydroxycyclohexenone
Authors: Brünjes Rainer , Tilstam Ulf , Winterfeldt Ekkehard 
Published: July 2007

AbstractThe Diels‐Alder adduct obtained by addition of quinone to the chiral cyclopentadiene 2 undergoes regioselective and stereoselective reduction after hydrogenation. The 4‐hydroxy ketone 3 thus formed yields the title compound 1 in a thermal retro Diels‐Alder process.
Beiträge zur Chemie des Bors, 208 Reaktionen eines Amino‐imino‐borans mit Phosphin‐, Phosphon‐ und Phosphorsäuren
Authors: Nöth Heinrich , Schübel Jürgen 
Published: July 2007

Reactions of an Amino Imino Borane with Phosphinic, Phosphonic, and Phosphoric AcidsControlled 1:1 reactions of R2P(O)OH with tmp – B = NtBu (1) (tmp = 2,2,6,6‐tetramethylpiperidino group) in hexane leads to R2P(O)OB(tmp)NHtBu (2). In most other cases mixtures of 2 with other products are obtained. Application of a 4:1 ratio of Me2P(O)OH and 1 results in the formation of pure [tBuNH3][B(OP(O)Me2)4] (3). Reaction of phosphonic acids with 1 in hexane at about –30°C leads preferentially to the addition of the acid to produce RP(O)[OB(tmp)NHtBu]2 (4), while H3PO4 reacts with 1 to yield OP[OB(tmp)NHtBu]3 (6). Species containing tetracoordinated boron atoms are formed as well in dichloromethane as a solvent. Spectral data for the compounds 2, 4, and 6 reveal three‐coordinate boron atoms, confirmed by an X‐ray structure analysis of 2a (R = CH3). This compound displays a fairly large B – O – P bond angle, 140.6(3)°.
Notiz/Note P4O7 und P4O6S, Vergleich der Molekül‐ und Kristallstrukturen
Authors: Frick Frank , Jansen Martin , Bruna Pablo J. , Peyerimhoff Sigrid D. 
Published: July 2007

P4O7 and P4O6S, Comparison of Molecular and Crystal StructureSingle crystals of P4O6S were grown for the first time. By X‐ray diffraction the space group (P21/c), the unit cell [α = 813.5(1), b = 938.3(1), c = 993.1(1) pm; β = 90.27(1)°], and the crystal and molecular structure have been determined. As compared to P4O7, the geometry of the P4O6 cage remains virtually unchanged upon substitution of the terminal oxygen atom by a sulfur atom. Calculated charge distributions clearly confirm the experimental results. With the exception of P(1), to which the additional chalcogen atom is attached, the effective charges at all other atoms seem not to be affected by an exchange of the terminal oxygen atom by a sulfur atom.
Structures of Tris(donor)‐Tris(acceptor)‐Substituted Benzenes, 1. Steric, Polar and Hydrogen‐Bonding Effects in Triaminotrinitrobenzenes
Authors: Jens Wolff J. , Nelsen Stephen F. , Petillo Peter A. , Powell Douglas R. 
Published: July 2007

AbstractThe X‐ray analyses of three 1,3,5‐tris(alkylamino)‐2,4,6‐trinitrobenzenes (alkyl = iPr, neopentyl, tBu; 1d – f) show their benzene rings to be highly distorted towards boat (1d iPrNH2) and twist‐boat (1e,f) forms. The patterns found for intramolecular donor‐acceptor interaction and hydrogen bonding depend on the conformation of the benzene core: boat structures have the “stern” amino group strongly donating to the “bow” nitro group in the para position and two stronger hydrogen bonds between the substituents on the “side” of the boat, whereas twist‐boat structures have two amino groups strongly interacting with the nitro group in their common ortho position to which there are also two strong hydrogen bonds. 1d – f undergo conformational exchange on the 13C‐NMR time scale at room temperature. Cooling to 220 K allows detection of all carbon signals and shows C1 symmetry to be present. AM1 calculations reproduce the distortions of 1d – f. Computations on several 2,4,6‐tridonor‐substituted 1,3,5‐trinitrobenzenes indicate that the pronounced deviations from planarity in 1a – f originate largely from electronic effects.
Lösliche bisaxial substituierte (Phthalocyaninato)ruthenium‐Komplexe
Authors: Hanack Michael , Vermehren Petra 
Published: July 2007

Soluble Bisaxially Substituted (Phthalocyaninato)ruthenium ComplexesSeveral attempts to prepare (tBu4Pc)Ru only led to an impure product (tBu4Pc)RuLx. This reacts quantitatively with pyridine to form (tBu4Pc)Ru(py)2, easily purified by chromatography. In addition the preparation of (tBu4Pc)RuL2 with L = pyridine, 2‐picoline (2‐pic), 3‐picoline (3‐pic), 4‐picoline (4‐pic), 2,5‐lutidine (2,5‐lut), and 2,6‐lutidine (2,6‐lut), respectively, is described. All complexes are characterized by spectroscopic methods including 1H‐NMR spectroscopy. Not even in the cases of (tBu4Pc)RuL2 with L = 2‐pic and 2,5‐lut, a careful removal of the ligands L by thermogravimetric methods (TG/DTA) leads to pure (tBu4Pc)Ru. For comparison, the bisadducts PcRuL2 with L = pyridine, picolines (2‐pic, 3‐pic, 4‐pic), lutidines (2,3‐lut, 2,5‐lut, 2,6‐lut), and chloropyridines (2‐Clpy and 3‐Clpy), respectively, are prepared by treatment of PcRu with an excess of the ligand. For the first time (phthalocyaninato)iron complexes PcFeL2 with sterically hindered axial ligands, e.g. PcFe(2‐pic)2, are prepared and characterized by 57Fe Mößbauer spectroscopy.
o‐(α‐Benzotriazolylalkyl)phenols: Versatile Intermediates for the Synthesis of Substituted Phenols
Authors: Katritzky Alan R. , Lan Xiangfu , Lam Jamshed N. 
Published: July 2007

AbstractPhenols and naphthols are benzotriazolylmethylated by 1‐(hydroxymethyl)‐1H‐benzotriazole (13) (a formaldehyde derivative) in the o‐ or (if both o‐positions are occupied) in the p‐position. The reaction can be extended to other aldehydes in the case of the naphthols. The methylene group in the o‐(benzotriazolylmethyl)phenols can be lithiated (but only after trimethylsilyl protection of the hydroxy group) and then substituted by various electrophiles. The benzotriazole residues in both the primary products and in their substituted derivatives can be displaced by the alkyl anions of Grignard reagents or by hydride ions allowing the elaboration of many new types of substituted phenols.