bluuebunny/crossref_metadata_2025_split huggingface dataset:
Preparation and Structure of Hexakis[(trialkylphosphane)aurio(I)]methanium(2+) Salts [(LAu)6C]2+(X‐)2 with LEt3P, iPr3P and XBF4‐, B3O3F4‐
Authors: Schmidbaur Hubert , Brachthäuser Benno , Steigelmann Oliver , Beruda Holger 
Published: July 2007

AbstractHexaaurated carbon complexes of the type [(R3PAu)6C](BF4)2, REt (2a), iPr (2b) have been prepared by the reaction of the appropriate (phosphane)gold(I) chlorides R3PAuCl (1a and 1b) with tetrakis(dimethoxyboryl)methane, 13C–enriched at the central carbon atom, in the presence of excess of CsF in HMPT at room temperature. The products 2a and 2b are characterized by standard spectroscopic methods including direct detection of the interstitial C atoms by 13C–NMR spectroscopy. The crystal structure of the compound [(iPr3PAu)6C](B3O3F4)2 · 3 CH2Cl2 (3), obtained from partial (anion) hydrolysis has been determined. It contains dications with a central carbon atom surrounded by six (phosphane)gold(I) units. The edges of the CAu6 octahedron represent short Au–Au contacts (aprox. 3.0 Å), which strongly contribute to the formation and stability of these hypercoordinated species. Attempts to prepare a corresponding hexaauriomethanium dication starting from tBu3PAuCl (1c) failed owing to the bulkiness of the (tri‐tert‐butylphosphane)gold(I) unit. The X–ray structure analysis for 1c verifies an extremely crowded environment of the gold atom with small Au—P—C angles of only 107° leading to efficient shielding of the metal atom by methyl groups.
Ergiebige Herstellung von (R)‐ und (S)‐3,3,3–Trifluormilchsäure und von (R)‐ und (S)‐(Trifluormethyl)oxiran
Authors: Bussche–Hünnefeld Christoph Von Dem , Cescato Claudio , Seebach Dieter 
Published: July 2007

Simple Access to (R)‐ and (S)‐3,3,3–Trifluorolactic Acid and to (R)‐ and (S)‐(Trifluoromethyl)oxiraneEthyl trifluoropyruvate (from hexafluoropropylene oxide) is reduced by NaBH4 to rac‐trifluorolactic acid which is resolved on a 100–g scale by salt formation with (R,R)‐ and (S,S)‐2–amino–1‐phenyl–1,3–propanediol (readily available intermediates of industrial chloroamphenicol synthesis). The enantiomerically pure trifluorolactic acids (>99% ee by GC analysis on cyclodextrin columns) are converted into (R)‐ and (S)‐(trifluoromethyl)oxirane in an overall yield of 73% by the following steps: esterification, THP protection of the OH group, LAH reduction and mesylation to the 2–THP–protected mesylate of 3,3,3–trifluoro–1,2–propanediol, and one–pot deprotection (Dowex 50) and cyclization (NaOCH2CH2OH) in ethylene glycol. The enantiomeric purity of the oxirane (b.p. 39C, isolated on a 10–g scale) was determined by GC to be >99%. Possible synthetic targets are mentioned which should be accessible in enantiomerically pure form from the (trifluoromethyl)oxirane described here.
Thermolabile Kohlenwasserstoffe, 32. Konkurrierende Cope‐;Umlagerung und Homolyse von meso‐ und DL‐3,4‐Di(1‐cyclohexen‐1‐yl)‐2,2,5,5‐tetramethylhexan
Authors: Herberg Clemens , Beckhaus Hans‐;Dieter , Kürtvelyesi Tamas , Rüchardt Christoph 
Published: July 2007

Thermolabile Hydrocarbons, 32. — Competing Cope‐;Rearrangement and Homolytic Decomposition of meso‐ and DL‐3,4‐Di(1‐cyclohexen‐1‐yl)‐2,2,5,5‐tetramethylhexanemeso‐ and DL‐3,4‐di(1‐cyclohexen‐1‐yl)‐2,2,5,5‐tetramethylhexane (3a) were prepared by an improved reduction procedure (Li/C2H5NH2) from meso‐ and DL‐2,2,5,5‐tetramethyl‐3,4‐diphenylhexane. Products of two competing thermal transformations, C — C cleavage vs. Cope rearrangement, were isolated and identified. From a kinetic analysis of this system of reactions, characteristic activation enthalpies and entropies were obtained for the competing transformations. The standard heat of formation of meso‐3a (ΔHf0(g) = –58.4 ± 1.2 kcal/mol) was determined by combustion calorimetry and by measurement of its heat of sublimation. A strain enthalpy Hs (meso‐ 3a) = 10.2 ± 1.2 kcal/mol was derived therefrom. Force‐field calculations of the diastereomers of 3a and the Cope products 8a were performed by using MM2, MM2ERW, and MM3 in order to analyse the conformational situation. The calculated ΔHf0(g) values for meso‐3a are higher than the experimental value by 4.4 (MM2), 5.2 (MM2ERW), and 14.5 (MM3) kcal/mol. Obviously, the three computational methods require reliable parameters for highly branched olefins like 3a and 5a. From the experimental heat of formation ΔHt0(g) and strain enthalpy Hs of meso‐3a and its ΔH* of homolysis the stabilization energy of the allylic radical 4 was determined to be 12.6 ± 1.5 kcal/mol.
3a,6‐Dihydro‐3H‐imidazo[1,2‐d]tetrazole aus 1‐ und 4‐Phenacyl‐1H‐tetrazolium‐Salzen und Ammoniak
Authors: Moderhack Dietrich , Bode Dirk‐;Ottfried , Schomburg Dietmar 
Published: July 2007

3a,6‐Dihydro‐3H‐imidazo[1,2‐d]tetrazoles from 1‐ and 4‐Phenacyl‐1H‐tetrazolium Salts and AmmoniaTreatment of the tetrazolium salts 1 with aqueous ammonia affords the novel ring system 2 (in certain cases along with the ylides 3). The structure of 2 has been confirmed by an X‐ray analysis of 2a.
Synthesis and Aggregation Properties in Solution of a New Octasubstituted Copper Phthalocyanine: {2,3,9,10,16,17,23,24‐Octakis‐[(dioctylaminocarbonyl)methoxy]phthalocyaninato}copper(II)
Authors: Duro José Antonio , Torres TomáS 
Published: July 2007

AbstractThe synthesis of the octasubstituted phthalocyanine1, highly soluble in organic solvents, is described. Its aggregation properties in different solvents and in the presence of alkaline, alkaline earth, and ammonium salts are studied.
Modellreaktionen zur Verankerung von Molybdän‐und Vanadium‐Oxiden auf Silicium‐Sauerstoff‐Oberflächen
Authors: Gosink Hans‐Jürgen , Roesky Herbert W. , Noltemeyer Mathias , Schmidt Hans‐Georg , Freire‐Erdbrügger Cristina , Sheldrick George M. 
Published: July 2007

Model Reactions to Anchor Molybdenum and Vanadium Oxides on Silica‐Oxygen SurfacesThe eight‐and twelve‐membered ring compounds [(tBu)21‐Si(O)2MoO2]2 (1) and [(tBu)2Si(O)2V(O)Cl]3 (2) have been prepared by the reaction of di‐tert1‐butylsilanediol or its dilithium salt with MoO2Br2 or VOCl3, respectively. Single crystal X‐ray structure analyses of 1 · 2 py and 2 have been performed. Crystals of 1 · 2 py contain two molecules of 1 · 2 py and four additional molecules of pyridine in the unit cell.
Monomeric Aldimino‐diorganoboranes and Aspects of Their Chemistry
Authors: Yalpani Mohamed , Köster Roland , Boese Roland 
Published: July 2007

AbstractThe hydroboration of benzo‐, tolu‐, p1‐methoxybenzo‐, or pivalonitriles with bis(9‐borabicyclo[3.3.1]nonane) (9H‐9‐BBN)2 affords the corresponding 9‐aldimino‐9‐borabicyclo[3.3.1]1‐nonanes (1a — d) in about 80% yields. Compounds 1a and 1d readily react with an excess of (9H‐9‐BBN)2 to form the 1:1 adducts 2a or 2d, respectively, containing a NB2H four‐membered ring (X‐ray structure of 2a). The adducts 2 are thermally rather stable. Compound 2a is converted to benzylbis(1,5‐cyclooctanediylboryl)amine (3a) only after 48 h at reflux in mesitylene. Compounds 1a — d are stable towards strong N‐bases. Compound 1d reacts with Et2O · BF3 to form 9‐fluoro‐9‐borabicyclo[3.3.1]nonane (4) and the 1:1 cyclic adduct (5d) of (2,2‐dimethylpropylideneamino)difluoroborane (6d) and 1d.
Übergangsmetallaktivierte organische Verbindungen, XXXVII. über eine neue Aldehyd‐und Ketonreaktion: Synthese und spektroskopische Untersuchung von α1‐Phosphonioalkoxy‐übergangsmetallkomplexen
Authors: Kauffmann Thomas , Abel Thomas , Schwarze Dieter 
Published: July 2007

Transition Metal‐Activated Organic Compounds, XXXVII[1]. — A Novel Reaction of Aldehydes and Ketones: Synthesis and Spectroscopic Investigation of α1‐Phosphonioalkoxy Transition Metal ComplexesHerrn Professor Ulrich Schöllkopf zum 65. Geburtstag gewidmet.
By treatment of aldehydes and ketones with one mole equivalent of a Lewis acid (TiCl4, NbCl5, TaCl5) and one mole equivalent of PPh3, or in one case of Ph2PCH2CH2PPh2, the aldehyde derivates [R1CH(P+Ph2R2)–OMCln]Cl– (4–8; MTi, Nb, Ta; R2Ph or CH2CH2PPh2) and the ketone derivatives [R1R2C(P+Ph3)–ONbCl4]Cl– (9–10) were prepared. Complexes 4–10 were isolated as air‐and water‐sensitive solids. According to the NMR spectra some of the obtained aldehyde derivatives 4–8 exist in solution as a mixture of isomers or oligomers, whereas the ketone derivatives 9 and 10 form in solution an equilibrium with the free ketone and the complex NbCl5 · PPh3. The chloride ion of 4–10 is perhaps coordinated to the metal.
Oxidative Desilylation of a 5,6:7,8‐Bis(dimethylsilyldioxy)[4]radialene
Authors: Maas Gerhard , Fronda Antonio 
Published: July 2007

AbstractThe title [4]radialene 1 reacts with N1‐methyltriazolinedione or with the iodine(III) salt PhI+ O+IPh · 2 BF4– in CH2Cl2 by oxidative elimination of only one dimethylsilyl unit to form the functionalized 3,4‐bis(alkylidene)1‐1‐cyclobutene 2 or its hydrolysis products, (Z)‐4 and (E)‐4. When the iodonium salt is used in CCl4, rearrangement of the radialene framework occurs, and the bicyclic fluorodimethylsilyl enol ether 9 is obtained. An X‐ray crystal structure analysis of 9 indicates a weak coordination between a carbonyl oxygen atom and a silyl group.
Reactions of cis1‐Stannyl‐boryl‐alkenes with Sulfur Bis(trimethylsilylimide) and N1‐Sulfinyl(trimethylsilyl)amine – X‐ray Analysis of an 1‐Amino‐1λ41‐thia‐2‐azonia‐3‐borata‐1,4‐cyclopentadiene
Authors: Wrackmeyer Bernd , Wagner Klaus , Boese Roland 
Published: July 2007

AbstractNew heterocyclic systems (1‐amino‐1λ41‐thia‐2‐azonia‐3‐borata‐1,4‐cyclopentadienes 4a and 4b, a 1λ41‐thia‐2‐aza‐3‐bora‐1‐cyclopentanone 7 and a 1‐trimethylstannyloxy‐1λ41‐thia‐2‐azonia‐3‐borata‐1,4‐cyclopentadiene 8) are formed by reaction of (E)1‐2‐diethylboryl‐1‐trimethylstannyl‐1‐butene (1a) and (E)1‐3‐diethylboryl‐2‐trimethylstannyl‐2‐pentene (1b) with sulfur bis(trimethylsilylimide) (2) and N1‐sulfinyl(trimethylsilyl)amine (3). There is a marked influence of other substituents at the CC bond on the product distribution. It appears that all reactions proceed via an intermediate borane adduct A. In A the proximity of the electrophilic site of 2 or 3 to various reactive sites of the alkene derivative opens the way to the final products. The proposed structures are supported by consistent 1H‐, 11B‐, 13C‐, 29Si‐and 119Sn‐NMR data. In the case of compound 4a an X‐ray analysis has been carried out.
Phosphanalkylene, 53. Synthese von α,β1‐ungesättigten Cycloalkanonen aus Bis[(1‐acylalkyliden)1‐triphenylphosphoranen] – Eine Methode zur Überführung von Carbonsäure‐Anhydriden in carbocyclische und heterocyclische Verbindungen
Authors: Bestmann Hans Jürgen , Pichl Rainer , Zimmermann Reiner 
Published: July 2007

Phosphane Alkylenes, 53[1]. – Synthesis of α,β1‐Unsaturated Cycloalkanones from Bis[(1‐acylalkylidene)triphenylphosphoranes] – A Method for the Transformation of Acid Anhydrides into Carbocyclic and Heterocyclic CompoundsAlkaline hydrolysis of bis[(1‐acylalkylidene)triphenylphosphoranes] 3 leads to 2‐cycloalken‐1‐ones 6. Intramolecular Wittig reaction of an intermediately formed monoacyl ylide 4 and intramolecular aldol condensation of a diketone 5, resulting from hydrolysis of both ylide functions, are discussed as possible reaction mechanisms. The oxidation of 3 with H2O2 · Ph3PO yields 7‐ and 8‐membered 2‐cycloalkene‐1,4‐diones 12, presumely via mono ylides 11 carrying an aldehyde group in the Ō‐position. The reactions of 3 with aldehydes (molar ratio 1:1) lead to the formation of mono Wittig compounds 15 which can cyclize affording 5‐ and 6‐membered 3‐alkenyl‐2‐cycloalken‐1‐ones 16. Since the ylides 3 are easily available from acid anhydrides the reaction sequences represent versatile approaches for the transformation of acid anhydrides into 2‐cycloalken‐1‐ones.
Neue zwitterionische λ51‐Spirosilicate: Synthesen, Einkristall‐Röntgenstrukturanalysen und Festkörper‐NMR‐Untersuchungen
Authors: Tacke Reinhold , Lopex‐Mras Angel , Sperlich Jörg , Strohmann Carsten , Kuhs Werner F. , Mattern Günter , Sebald Angelika 
Published: July 2007

New Zwitterionic λ51‐Spirosilicates: Syntheses, Single‐Crystal X‐Ray Structure Analyses, and Solid‐State NMR StudiesThe zwitterionic spirocyclic λ51‐silicates bis[3,4,5,6‐tetrabromo‐1,2‐benzenediolato(2‐)][2‐(pyrrolidinio)ethyl]silicate (5; and its monohydrate 5 · H2O) and bis[1,2‐benzenediolato(2–)]1‐[(dimethylammonio)methyl]silicate (6) were synthesized by various methods including Si – C bond cleavage reactions. The crystal structures of 5, 5·H2O, and 6 were investigated by X‐ray diffarction. Furthermore, 5, 5·H2O, 6, and the related zwitterionic λ51‐spirosilicates 1·1/4 CH3CN, 2·CH3CN, 3·CH3CN, and 4 were characterized by solid‐state NMR spectroscopy (29Si and 15N CP/MAS). The pentacoordinate silicon atoms of 5, 5·H2O (two cystallographically independent zwitterions and two crystallographically independent water molecules), and 6 (two crystallographically independent zwitterions) are surrounded by four oxygen atoms and one carbon atom. The coordination polyhedrons around the silicon atoms of 5 and 6 can be described as distorted (5) or nearly ideal (6) trigonal bipyramids, the carbon atoms being in equatorial positions. 5 forms intramolecular and 6 intermolecular (→ for‐mation of dimeric units) N – H…O hydrogen bonds. The co‐ordination polyhedrons around the two crystallographically independent silicon atoms of 5·H2O can be described as a nearly ideal and slightly distorted square pyramid, respectively, the carbon atoms being in the apical positions. In the crystal lattice of 5·H2O, intermolecular N – H…O O – H…O hydrogen bonds between the zwitterions and water molecules are observed. The results obtained by X‐ray diffraction and solid‐state NMR spectroscopy are consistent for each compound studied.
Struktur und Dynamik von Lanthanoid‐Tetraazacyclododecantetraacetat‐(DOTA‐)Komplexen in Lösung
Authors: Hoeft Simone , Roth Klaus 
Published: July 2007

Structure and Dynamics of Lanthanoid Tetraazacyclododecanetetraacetate DOTA Complexes in SolutionIn aqueous solution lanthanoid DOTA complexes exist as a mixture of two stereoisomers, and their structures have been determined from the dipolar parts of the observed 1H‐NMR chemical shifts for EuDOTA and YbDOTA. The relative concentration of the δ(δδδδ) isomer decreases with decreasing ionic radius. For EuDOTA a 1:4 mixture is observed, and the main isomer has a δ(λλλλ) structure which is also found in the solid state. Two independent intramolecular isomerizations were detected by 1H‐NMR Exchange Spectroscopy (EXSY). The faster process is the rotation of the four acetate substituents around the C–N bonds [δ(λλλλ)→δ(λλλλ)isomerization]. The cyclododecane ring inversion is slower [δ(λλλλ)→δ(δδδδ) isomerization]. The intramolecular racemization of the δ(λλλλ) main isomer into its δ(δδδδ) enantiomer includes two successive isomerizations in a δ(λλλλ)→δ(λλλλ)→δ(δδδδ) sequence and is the slowest process.
Synthese und Reaktionen von (η51‐Pentamethylcyclopentadienyl)1‐ und (η51‐Ethyltetramethylcyclopentadienyl)titantrifluorid
Authors: Sotoodeh Mansoreh , Leichtweis Iring , Roesky Herbert W. , Noltemeyer Mathias , Schmidt Hans‐Georg 
Published: July 2007

Preparation and Reactions of (η51‐Pentamethylcyclopentadienyl)1‐ and (η51‐Ethyltetramethylcyclopentadienyl)titanium Trifluoride[1]Compound Cp*TiCl3 (1, Cp*η51‐Me5C5) reacts with an excess of AsF3 to yield the crystalline complex [Cp*TiF3]2·2 AsF3 (2). AsF3 can be removed from 2 in vacuo to give Cp*TiF3 (3). Complex (η51‐EtMe4C5)TiCl3 (4) is converted by an excess of AsF3 to (η51‐EtMe4C5)TiF3 (5). Compound 3 reacts with a lithium 1,3‐diketonate to form the hexacoordinated complex (6) and with a lithium benzamidinate to yield pentacoordinated Cp*TiF2[(Me3SiN)2 C‐C6H4OMe‐(4)] (7): The reaction of 3 with Ph3PNSiMe3 and C2H2(Ph2PNSiMe3)2 leads to Cp*TiF2NPPh3 (8) and (Cp*TiF2NPPh2)2C2H2 (9), respectively. X‐Ray structure analyses of compounds 2 and 5–9 have been performed.
Metallorganische Lewis‐Säuren, XLVIII. Neue Vorläufer metallorganischer, kationischer Lewis‐Säuren mit zwei freien Koordinationsstellen: (OC)4Re(OEt2)FBF3 und (OC)2(PPh3)2Ru(FBF3)2
Authors: Krämer Roland , Lippmann Elisabeth , Noisternig Karin , Steimann Manfred , Nagel Ulrich , Beck Wolfgang 
Published: July 2007

Organometallic Lewis Acids, XLVIII[1]. – New Precursors to Organometallic Cationic Lewis Acids with two Accessible Coordination Sites: (OC)4Re(OEt2)FBF3 and (OC)2 (PPh3)2Ru(FBF3)2The allyl transfer reaction between Re(CO)5− and [(η31‐allyl)PdCl]2 complexes leads to (allyl)rhenium complexes (η31‐H2CCR1CR2R3) Re(CO)4 (1: R1, R2, R3H; 2; R2, R3H, R1Me; 3: R1, R2H, R3Me; 4: R1H, R2, R3Me). The 2‐methylallyl complex 2 has been characterized by low‐temperature X‐ray diffraction. Protonation of 1 with HBF4 · OEt2 in CH2Cl2 gives the complex (OC)4Re(OEt2)FBF3 (5), which is a precursor for the 14 e− System “(OC)4Re+”. THF and H2O replace the diethyl ether in 5 to give [(OC)4Re(solvent)2]BF4 (6, 7). The reaction of (OC)2(PPh3)2RuCl2 with AgBF4 yields the complex (OC)2 (PPh3)2Ru(FBF3)2 (8), which can be considered as a precursor for the 14 e− cation “(OC)2 (PPh3)2Ru2+” and reacts with H2O to give [(OC)2 (PPh3)2Ru(F)(H2O)]BF4 (9). Complexes 5–9 are characterized by IR, 1H‐, 13C‐, 31P‐and 19F‐NMR spectroscopy.
Tetraalkylhydrido‐und Tetraalkylmethyldialuminat(5) mit Aluminium – Aluminium‐Bindung: [R2Al – AlXR2]− {RCH(SiMe3)2; XH, Me}
Authors: Uhl Werner , Vester Annegret 
Published: July 2007

Tetraalkylhydrido‐and Tetraalkylmethyldialuminate(5) with Aluminium – Aluminium Bond: [R2Al – AlXR2]– {RCH(SiMe3)2; XH, Me}Tetrakis[bis(trimethylsilyl)methyl]dialuminium(4) (1) with an aluminium – aluminium bond reacts with tert1‐butyllithium in the presence of the chelating tetramethylethylenediamine (TMEDA) to give a hydridodialuminate(5) 2 [R2Al – AlHR2]− {RCH(SiMe3)2} by β1‐elimination and addition of the hydride anion to one aluminium atom. By treatment of 1 with methyllithium a similar product is formed containing a methyl group bound to aluminium: [R2A1 – AlMeR2]– 3. As shown by crystal structure determination the aluminium – aluminium bond of both molecules is not bridged. Instead, the compounds contain a saturated, four‐coordinated aluminium neighbouring an unsaturated, threefold coordinated aluminium atom. While in the hydrogen compound 2 the aluminium – aluminium bond length [266.7(3) pm] remains unaffected in comparison to the neutral starting compound 1, it is lengthened in the methyl derivative 3 by 9 pm to 275.2(3) pm probably due to the higher sterical demand of the methyl group.
Synthesis of Isomerically Pure Organodihydrofullerenes
Authors: Hirsch Andreas , Grösser Thomas , Skiebe Andreas , Soi Antonio 
Published: July 2007

AbstractControlled two‐step nucleophilic hydroalkylations, hydroar‐ylations as well as hydrostannylations of fullerene‐60 (1) and fullerene‐70 (2) lead to defined organodihydrofullerenes C60HR and C70HR. NMR investigations show that only one isomer of each organodihydrofullerene with Cs symmetry is formed. In all cases the addition takes place at a double bond separating two six‐membered rings of the fullerene core. In this way a variety of organodihydrofullerenes also carrying functional groups have been synthesized.
Oxidative Spaltung von Poly(o1‐phenylendiselenid)
Authors: Heckmann Gert , Wolmershäuser Gotthelf 
Published: July 2007

Oxidative Cleavage of Poly(o1‐phenylenediselenide)Poly(o1‐phenylenediselenide) is cleaved at the Se–Se bond by treatment with SOCl2 to give benzene‐1,2‐bis(selenenyl chloride) (2) and benzene‐1,2‐bis(selenium trichloride) (3), respectively. In the solid state 2 is dimerized by Se…Se bonds whereas 3 is monomeric having terminal as well as intramolecular bridging Cl atoms. Treatment of 2 with SbCl5 gives an ionic compound (4) with a dimeric cation exhibiting a weak SeSe bond and SbCl6– as a counterion 3 reacts with W(CO)6 to give trigonal prismatic dicarbonyl bis(o1‐phenylenediselenolato)tungsten (5).
Metallinduzierte und basenkatalysierte 2‐Propinyl‐Allenyl‐Umlagerung in [(HCCCH2)(2,4,6‐tBu3C6H2O)]PMoCP(CO)2
Authors: Leise Michael , Lang Heinrich , Imhof Wolfgang , Zsolnai Laszlo 
Published: July 2007

Metal‐Induced and Base‐Catalyzed 2‐Propynyl‐Allenyl Rearrangement in [(HCCCH2)(2,4,6‐tBu3C6H2O)]PMoCP(CO)2The synthesis and reactivity of [(HCCCH2)(2,4,6‐tBu31‐C6H2O)]PMoCp(CO)2 (3) is described. [(HCCCH2)(R)]PCl (1) reacts with NaMoCp(CO)3 (2) to afford the s̀3,λ41‐phosphanediyl compounds 3. With NEt3 a prototropic rearrangement of the 2‐propynyl ligand of 3 to an allenyl group in [(H2CCCH)(R)]PMoCp(CO)2 (5) is observed. However, with Cr(CO)5 · THF a metal‐induced rearrangement of the 2‐propynyl unit in 3 yields η3‐{(2,4,6‐tBu3C6H2O)[(CO)5Cr]PCHCCH2}MoCp(CO)2 (7). Complex 7 contains a 1‐phosphaallyl system, which is functionalized by an exocyclic CC double bond X‐ray structure analyses of 3 and 7 are performed.
(tert1‐Butylisonitril)kupfer(I)1‐Komplexe mit Acetylacetonato‐oder η51‐Cyclopentadienyl‐Liganden
Authors: Kruck Thomas , Terfloth Christian 
Published: July 2007

(tert1‐Butylisonitrile)copper(I) Complexes with Acetylacetonato‐or η51‐Cyclopentadienyl LigandsCopper(I) complexes of the type acacCu(CNtBu) (1) and CpCu(CNtBu) (2) are accessible by the reaction of [ClCu‐(CNtBu)]4 with M(β1‐diket) or MCp (MLi, Na, K, Tl), respectively. hfacCu(CNtBu)2 (3) and hfacCu(CNtBu)3 (4) are prepared by adding molar amounts of tBuNC to hfacCu(CNtBu) (1b).
Azabicyclononane durch Fragmentierung, II. Regiospezifische (Grob‐)Fragmentierung zur Darstellung von 3‐Azabicyclononanen
Authors: Risch Nikolaus , Billerbeck Ulrich , Meyer‐Roscher Bernd 
Published: July 2007

Azabicyclononanes by Fragmentation, II[1]. – Synthesis of 3‐Azabicyclononanes by Regiospecific (Grob) FragmentationClemmensen reduction of the non‐enolizable β1‐dioxo group in the 1‐azaadamantanedione derivative 1 gives the β1‐hydroxy ketone 2, which is converted to the thioesters 3. Treatment of 3a or 3b with nBu3SnH/toluene yields the partially deoxygenated monoketone 4. Chlorination of 2 with SOCl2 generates 6 (geminal dichlorination). Dehalogenation with nBu3SnH produces 5. On the other hand, 2 can be monochlorinated to give 7, selectively. Preparative Grob fragmentation of the aza‐tricyclic skeleton in 7 regiospecifically provides the 3‐azabicyclo[3.3.1]nonane derivative 8. An even better access to 8 from 2 proceeds via an intermediate tosylate.
Complexation with Diol Host Compounds, 12. Synthesis and Solid‐State Inclusion Properties of Bis(diarylhydroxymethyl)1‐Substituted 1,1′‐Binaphthyls. Crystal Structures of a Host and Its Pyridine Clathrate
Authors: Weber Edwin , Skobridis Konstantinos , Wierig Andreas , Barbour Leonard J. , Caira Mino R. , Nassimbeni Luigi R. 
Published: July 2007

AbstractA series of new clathrate host molecules1 – 8containing two bis(diarylhydroxymethyl) groups attached to different positions (2,2′ or 8,8′) of a 1,1′‐binaphthyl frame have been synthesized. Their clathrate formation properties with organic guests including alcohols, amines, ketones, and other dipolar aprotic compounds or aromatic hydrocarbons are reported (74 examples of clathrates) together with the results of solvent competition experiments for the parent host compound. The inclusion formation and the clathrate stoichiometries depend on the structure of the host molecules in a systematic manner. The crystal structures of the free parent host1and its pyridine clathrate (1 : 3) have been determined by X‐ray diffraction. The molecular structure of the host is similar in the two species involving an intramolecular hydrogen bond between the host hydroxyls. No other hydrogen bond is involved in the free host case while in the pyridine inclusion compound the second host hydroxyl forms a hydrogen bond with the nitrogen of one pyridine guest which is surrounded by two unbound pyridine species such as to form clusters of three pyridine guests enclosed in the cavities between the host molecules. Thermal analysis corresponds with the two binding states of the pyridine molecules in the clathrate.