bluuebunny/crossref_metadata_2025_split huggingface dataset:
(η8‐Cyclooctatetraene)(η4‐1,2‐ and ‐1,3‐diphosphacyclobutadiene)titanium: Preparation, Structure, and Reactivity
Authors: Binger Paul , Glaser Gerald , Albus Stefan , Krüger Carl 
Published: July 2007

AbstractThe synthesis of the (η8‐cyclooctatetraene)(η4‐1,3‐ and ‐1,2‐diphosphacyclobutadiene)titanium complexes 3a‐c and 4a, b by cyclodimerization of the phosphaalkynes 2a‐c [a: R = tBu, b: R = adamantyl (ad), and c: R = (iPr)(Me3Si)N] in the coordination sphere of the (η8‐cyclooctatetraene)titanium complex 1 is described. The molecular structures of 3a‐c and 4a, b were determined by spectroscopic methods (31P, 1H, and 13C NMR). In the case of 3a and 4a, X‐ray analyses were carried out. The increased reactivity of 4a compared to 3a was utilized to separate 3a from 4a. Displacement of the 1,2‐diphosphete (isolated as its cyclodimer 5) from 3b was achieved by reaction with hexachlorethane.
Stable Carbonyl‐ and Thiocarbonylrhodium(I) Complexes Containing s̀‐Bonded Phenyl and Vinyl Groups as Ligands
Authors: Wiedemann Ralf , Wolf Justin , Werner Helmut 
Published: July 2007

AbstractThe phenyl‐ and vinylrhodium(I) complexes trans‐[Rh(R)(CO)(PiPr3)2] (2, 3) were prepared from the chloro derivative 1 and Grignard reagents. The corresponding thiocar‐bonyl compound trans‐[Rh(CH=CH2)(CS)(PiPr3)2] (7) was obtained similarly from trans, ‐[RhCl(CS)(PiPr3)2] (6) and CH2=CHMgBr. The preparation of 6 occurred via trans‐ [RhCl(η2‐S=C=S)(PiPr3)2] (5) as intermediate. The carbonyl complexes 2 and 3 are quite inert in the presence of CO and do not react by migratory insertion to give acylrhodium derivatives.
Tin for Organic Synthesis, 14. Synthesis of Aromatic and α,β‐Unsaturated Aldehydes by a Friedel‐Crafts‐like Electrophilic Destannylation Using 1,1‐Dichloromethyl Methyl Ether
Authors: Niestroj Michael , Neumann† Wilhelm P. 
Published: July 2007

AbstractA mild and effective method for the preparation of a variety of aromatic (7a–m), heteroaromatic (7n–r), and α,β‐unsaturated aldehydes (8a–f) is described. The reaction of trialkylaryl‐ (2a–o), heteroaryl‐ (2p–t), and 1‐alkenylstannanes (4a–f and 5a–f) with dichloromethyl methyl ether (1, DCME) in the presence of aluminium trichloride followed by hydrolysis provides the corresponding aldehydes. In the case of arylstannanes the ipso‐isomers are generally formed; the p‐alde‐hydes occur as side products. The electrophilic substitution of 1‐alkenylstannanes with 1 leads to α,β‐unsaturated aldehydes in an ipso‐ and stereospecific manner. A comparison of the leaving abilities of the stannyl and silyl groups shows a lower or even zero reactivity of the silyl‐substituted compounds 6a–c towards the electrophile 1. In the silylstannylal‐kene 6c only the stannyl group reacts whereas the stannyl function remains unaffected in the product, aldehyde 11.
Phosphaniminato‐Komplexe des Arsens. Kristallstrukturen von [AsCl(NPMe3)]2Cl2, [AsCl(NPMe3)2SbCl4]SbCl6 und [AsCl(NPMe3)2SnCl4] · CH3CN
Authors: Garbe Ralf , Wocadlo Sigrid , Kang Hak‐Chul , Massa Werner , Harms Klaus , Dehnicke Kurt 
Published: July 2007

Phosphane Iminato Complexes of Arsenic. Crystal Structures of [AsCl(NPMe3)]2Cl2, [AsCl(NPMe3)2SbCl4]SbCl6, and [AsCl(NPMe3)2SnCl4] · CH3CN[AsCl(NPMe3)]2Cl2 (1) was prepared by the reaction of arsenic trichloride with the silylated phosphane imine Me3‐SiNPMe3 in acetonitrile solution. According to the crystal structure determination, 1 has an ionic structure with [AsCl(NPMe3)]22+ ions, in which the As atoms are linked by the μ2‐N atoms of the NPMe3– groups. Compound 1 reacts with antimony pentachloride to give [AsCl(NP‐Me3)2SbCl4]+SbCl6– (2), with tin tetrachloride to form [AsCl(NPMe3)2SnCl4] (3), which is isoelectronic to the cation of 2. In 2 and 3 AsCl(NPMe3)2 acts as a chelating agent forming and , respectively, four‐membered ring structures.
Synthesis and Structure of Metal‐Functionalized Phosphaarsiranes
Authors: Weber Lothar , Sommer Oliver , Stammler Hans‐Georg , Neumann Beate , Becker Gerd , Kraft Hans 
Published: July 2007

AbstractReaction of (η5‐C5Me5)(CO)2FeAs(SiMe3)2 (1) with equimolar amounts of (bis(trimethylsilyl)methylene]chlorophosphane afforded the 1‐metallo‐1‐arsa‐2‐phosphapropene (η5‐C5‐Me5)(CO)2FeAs(SiMe3)P=C(SiMe3)2 (2) in addition to a few crystals of dimetallophosphaarsirane (η5‐C5Me5)(CO)2Fe‐ AsC(SiMe3)2PFe(CO)2(η5‐C5Me5) (3). Treatment of 2 with an excess of [(Z)‐cyclooctene]Cr(CO)5 and subsequent chromatography furnished the phosphaarsirane‐[Cr(CO)5] adduct (η5‐C5Me5)(CO)2Fe‐ηAsC(SiMe3)2PH[Cr(CO)5] (5). The molecular structures of 3 and 5 were established by single‐crystal X‐ray structure analyses.
Nickel Hemiporphyrazines as Bisdienes and Bisdienophiles: Synthesis and Characterization
Authors: Rack Michael , Hauschel Bernd , Hanack Michael 
Published: July 2007

AbstractThe bisdienophilic (hemiporphyrazinato)nickel complexes 1a‐d bearing various alkoxy groups were synthesized from diiminoisoindoles 9a‐d, diaminopyridines 10a, d, and nickel acetate. Reaction of 1a‐d with an excess of pentaene 3 delivered the macrocyclic bisdienes 2a‐d. The hemiporphyrezines were characterized by 1H‐ and 13C‐NMR spectroscopy. The NMR spectra of the 1,6,16,21‐tetrabutoxy‐substituted compounds 1b and 2b are discussed with respect to the presence of syn/anti isomers.
Formation of Metallophosphenium Cluster Complexes: Synthesis and Structure of Cp(Ph)[N(SiMe3)2]
Authors: Reisacher Hans‐Ulrich , Duesler Eileen N. , Paine Robert T. 
Published: July 2007

AbstractThe reaction of [(Me3Si)2N](Ph)PW(CO)2Cp with Fe2(CO)9 produces in good yield the bimetallic compound Cp(Ph)[N(SiMe3)2] that was characterized by mass spectrometry, IR, 1H‐, and 31P‐NMR spectroscopy, and single crystal X‐ray diffraction analysis. The molecular structure consists of Fe(CO)3 and CpW(CO)2 fragments joined by a bridging CO ligand and a phosphenium ion fragment which comprise a four‐membered bicyclic structure.
The Catalytic Ring‐opening Cyclooligomerization (ROC) of Thietane by the Complexes M(CO)5L (M  Cr and W; L = CO, thietane and 1,5,9‐Trithiacyclododecane)
Authors: Adams Richard D. , Falloon Stephen B. , Perrin Joseph L. , Queisser Joachim A. , Yamamoto John H. 
Published: July 2007

AbstractThe following four compounds have been synthesized: M(CO)5L (3 and 4, where M = Cr and W, and L = H2), W(CO)5(12S3) (5, where 12S3 = 1,5,9‐trithia‐cyclododecane), and [W(CO)5]2(12S3) (6). The molecular structures of 4 and 5 were established by single‐crystal X‐ray diffraction analyses. Both compounds contain a W(CO)5 group coordinated to one of the sulfur atoms of the hetero‐cycle. The ability of the compounds M(CO)6, 1 and 2 (M = Cr and W), and 3 – 5 to catalytically produce ring opening cyclooligomerization (ROC) of thietane into 12S3 and 24S6, (24S6 = 1,5,9,13,17,21‐hexathiacyclotetracosane) has been investigated. Compounds 1 – 3 have relatively low activity. Compounds 4 and 5 have the highest activity and selectivity for 12S3 formation. Crystal Data for 4: space group = P212121, a = 12.906(2) Å, b = 13.730(4) Å, c = 6.427(1) Å, Z = 4, 1306 reflections, R = 0.033; for 5: space group = P1¯, a = 12.703(1) Å, b = 13.510(2) Å, c = 5.833(1) Å, α = 101.75(1)°, β = 97.54(1)°, γ = 101.70(1)°, Z = 2, 2225 reflections, R = 0.023.
[Bis(phosphonio)isophosphindolide]silver Complexes
Authors: Gudat Dietrich , Schrott Martin , Bajorat Volker , Nieger Martin , Kotila Sirpa , Fleischer Roland , Stalke Dietmar 
Published: July 2007

AbstractThe outcome of reactions of bis(phosphonio)isophosphindolide salts 1[X] and 6[X] (X‐  Cl‐, Br‐, CF3SO3‐) with silver salts AgY (Y‐ = CF3SO3‐, CF3CO2‐, CH3CO2‐, 1/2 SO4‐) depends strongly on the available anions X, Y. If X‐, Y‐  CF3SO3‐, both mononuclear and dinuclear silver complexes are formed which exhibit either μ1,μ1(P) or μ2,η1(P) coordination of the cations 1, 6 to one or to both metals. In solution, dynamic equilibria between both types of products and free 1, 6 were detected by 31P‐NMR spectroscopy. Mononuclear (4a, 7) and dinuclear (5a, 8) complexes were isolated as solvates with CHCl3 or THF. If X‐, Y‐ = CF3CO2, only equilibrium mixtures between the free ligands and silver complexes and no isolable products were obtained. 31P‐NMR investigations revealed a preference for the formation of dinuclear complexes. Anion metathesis and precipitation of AgX were observed for X‐ = Cl‐, Br‐. No coordination of 1, 6 to Ag+ took place in the case of Y‐  CH3CO2‐, SO42‐. The formed complexes were characterised in solution by 31P‐ and in part by 109Ag‐NMR spectroscopy. Complexes 7, 8 were further studied by single crystal X‐ray diffraction which revealed the presence of a THF molecule coordinated to silver in both cases. The μ2‐coordinated cation 1 is the only bridging ligand in 8, whereas the presence of additional μ2‐CF3CO2 ligands was deduced from the results of 31P,31P EXSY measurements in the case of the trifluoroacetato complexes.
Diastereoselective Substitution of PR3 for CO in Carbohydrato‐ and Menthyloxycarbene Complexes of Manganese – Synthesis of Chiral‐at‐metal Carbene and Carbyne Complexes
Authors: Fischer Helmut , Schleu Joachim 
Published: July 2007

AbstractThe substitution of PR3 (R = C6H4CH3‐p, C6H4Cl‐p, C6H11,OCH3) for a CO ligand in chiral carbohydratocarbene complexes [(η5‐C5H5)(CO)2MnC(OR*)Ph] [OR* = α‐ (1α) and β‐mannofuranosyl (1β), (–)‐menthyloxy (9)] proceeds diastereoselectively. The diastereoselectivity depends on PR3 and on the OR* substituent and ranges from 12% de (R = OCH3) to 80% (R = C6H4CH3‐p). In contrast, the reaction of 1β with P(OPh)3 is non‐selective. The diastereoselectivity generally increases with increasing nucleophilicity of PR3 and decreases in the series 1β > 1α > 9. The highest diastereoselectivity was observed in the reaction of 1β with P(C6H4CH3‐p)3. Predominantly, the isomer with the (S) configuration at the metal [(S Mn)‐2β] was formed which could be separated from the diastereomeric mixture by chromatography and be obtained in a pure form. Subsequent reaction of (SMn)‐2β with BF3 afforded the carbyne‐manganese complex (SMn)‐[(η5‐C5H5){P(C6H4CH3‐p)3}(CO)MnCPh]BF4.
Derivate des Imidazols, XVII. Synthese und Eigenschaften von Dichlor(1,3‐dimethyl‐2‐imidazol‐2‐ylidenimino)‐phosphan – ein Methylenamino‐Substituent mit ungewöhnlichen Donoreigenschaften
Authors: Kuhn Norbert , Fawzi Riad , Steimann Manfred , Wiethoff Jörg 
Published: July 2007

Imidazole Derivatives, XVII. – Synthesis and Properties of Dichloro(1,3‐dimethyl‐2‐imidazol‐2‐ylidenimino)phosphane – a Methylenamino Substituent with Uncommon Donor PropertiesDichloro(1,3‐dimethyl‐2‐imidazol‐2‐ylidenimino)phosphane (5) is obtained from 1,3‐dimethyl‐2,3‐dihydro‐2‐trimethylsilyliminoimidazole (4) and PCl3 in almost quantitative yield. Strong PN‐π interaction (5B) is revealed by its X‐ray structure analysis [P(1)–N(1) 1.579(2) Å]. AlCI3 causes chloride abstraction to give the cationic cyclophosphazane 8 identified by NMR spectroscopy.
Paramagnetic Planar Complexes of NiII: Influence of R and R′ on the Formation, Coordination Geometry and Magnetic Properties of Phosphinic Amidato Bischelates [R2P(O)NR′]2Ni
Authors: Brück Arno , Englert Ulli , Kuchen Wilhelm , Peters Wilfried 
Published: July 2007

AbstractAfter a brief review of previous work the results of the metathesis reaction between Ni(dme)Br2 and R2P(O)NR′Li [R = tBu, iPr, Ph; R′ = Et, Pr, iPr, (±)‐sBu, tBu, tPen, Cy, Ph, (–)‐α‐methylbenzyl = Mb, 1‐adamantyl = Ad] are reported. Complex formation occurred only with lithiated amides of tert‐butylphosphinic acid, and bischelates [tBu2P(O)NR′]2Ni were obtained when R′ = sBu, Mb, tPen, Ad (1d – g). With R′ = Et, Pr bischelation was incomplete. Vis spectroscopy showed the paramagnetic compounds 1d – f to be planar in the solid state but tetrahedral in solution. 1g is tetrahedral in both phases. The planar structure of 1f was confirmed by X‐ray single‐crystal analysis (monoclinic, space group P21/n). The magnetic moments μeff of 1d, e, g are ca. 3.2–3.5 μB in both phases and the Curie‐Weiss law is obeyed in the range 293–183 K. The same is valid for dissolved 1f. The μeff values of solid 1f are however, strongly temperature‐dependent, varying from 1.38 to 0.55 μB (300–90 K). NMR data (31P, 1H, 13C) are reported. Obviously, a favorable combination of electronic and steric factors of substituents R and R′ produces with ligands [R2P(O)NR′]– the donor quality necessary for bischelation as well as the singular field strength required for the formation of planar paramagnetic species. As the combination of paramagnetism and planarity is bound to the solid state, lattice energy effects may be finally decisive for this unique constellation of tetracoordinated NiII complexes.
Synthesis, Structure, and Magnetic Properties of a 2,2‐Dipyridyl‐2,5‐dihydro‐imidazole‐1‐oxyl‐(L‐)Bridged Disilver Complex [Ag2L2](SbF6)2: A Four‐Membered Ring from two Ag(I) Ions and two Imine Nitrogen Atoms
Authors: Hintermaier Frank , Mihan Shahram , Gerdan Michael , Schünemann Volker , Trautwein Alfred , Beck Wolfgang 
Published: July 2007

AbstractThe reaction of 2,5‐dihydro‐4,5,5‐trimethyl‐2,2‐di‐2‐pyridyl‐imidazole‐1‐oxyl (L) with AgSbF6 gives the complex [Ag2L2]2+[SbF6–]2 which was characterized by X‐ray diffraction. – The complex (a biradical) forms a four‐membered ring with two Ag(I) ions and two imine nitrogen atoms of the imidazolines with a relatively short Ag – Ag distance [2.839(2) Å]. Magnetic measurements indicate that two nitroxide radicals are slightly coupled.
Chiral Organometallic Reagents, XX. An Enantiomerically Enriched (α‐Phenylselenoalkyl)magnesium Compound
Authors: Klute Wolfgang , Krüger Michael , Hoffmann Reinhard W. 
Published: July 2007

Abstractα‐Selenoalkyl Grignard reagents 2 are chiral. On reaction with the magnesium chelate 3a of α‐benzyloxypropionaldehyde they show significant degrees of kinetic resolution, especially when the reactions are run in CH2Cl2. Under these conditions, racemic 2 was resolved by reaction with 0.59 equivalents of 3a at temperatures below –20°C. The remaining 2 had an enantiomer enrichment of 80–86% e.e. (as found by trapping). Hence, 2 has a considerably higher configurational stability than its lithium counterpart 1.
Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCIII. Diosma[5.n.5.n]ortho‐, ‐meta‐, and ‐paracyclophanes (n = 0–2)
Authors: Lindner Ekkehard , Pitsch Markus W. , Fawzi Riad , Steimann Manfred 
Published: July 2007

AbstractThe reaction of the ortho‐, meta‐, and para‐bis(triflates) [(F3CSO2OCH2CH2C6H4)2(CH2)n] with n = 0 (ortho: 1a), n = 0, 1 (meta: 1b, d), and n = 0–2 (para: 1c, e, g) with [Os(CO)4]2– results in the formation of the diosma[5.n.5.n]‐ortho‐, ‐meta‐, and ‐paracyclophanes with n = 0 (ortho: 2a), n = 0, 1 (meta: 2b, d), and n = 0–2 (para: 2c, e, g). On reaction of the bis(triflates) 1a, b with the dianionic [Fe(CO)4]2– the corresponding ferracyclophanes are formed only in situ. Carbon monoxide insertion into the Fe–C s̀ bonds of the ferracycles affords the ketones 6a, b. The structures of 2a and 2e were investigated by X‐ray structural analysis. Compounds 2a and 2e crystallize in the space group P21/c with Z = 8 and P1 with Z = 2, respectively.
Dithio and Thiono Esters, 62. Reactions of Alkanedithioic Acid Dianions with Iodine, Sulfur, and Tin Compounds
Authors: Hartke Klaus , Wagner Uwe 
Published: July 2007

AbstractThe monoanion of the alkanedithioic acid 1a is oxidized with hypervalent iodine compounds to form the 1,2‐dithiine 6, the monoanion of 1b yields the 1,2,4‐trithiolane 7 and the dianions 2b, c furnish the 1,2,4,5‐tetrathianes 3b, c. With diphenyltin or dimethyltin dichlorides 8 the monoanions of 1b, c afford the monothioacyl or bisthioacyl organotin sulfides 10a–c or 11a, b respectively. When treated with lithium hexamethyldisilazane, 10b undergoes an intramolecular cyclization to the 1,3,2‐dithiastannetane 9b; 10a is deprotonated by triethylamine to the 1,3,5‐trithia‐2‐stanninane 13. The dianion 2c reacts with diphenyltin dichloride 8 to yield the 1,3,2‐dithiastannetane 9d, with dimethyltin dichloride the 1,2,4‐trithiolane 16 is formed. 9d is cleaved by thionyl chloride, sulfur dichloride, and disulfur dichloride to give a complex mixture of the 1,2,4,5‐tetrathiane 3c and the cyclic polysulfides 1,2,3,4,5,6‐hexathiepane 18, 1,2,3,5,6,7‐hexathiocane 19 and the 1,2,3,5,6‐pentathiepane 20 in varying amounts. Reaction of the dianion 2b with thionyl chloride leads to the formation of the 1,2,4,5‐tetrathiane 3b as main product; byproducts are cyclic polysulfides, the 1,2,3,5,6‐pentathiepane 21 and the 1,2,3,4,5,6‐hexathiepane 22.
Synthesis and Structure of Methoxybis[tris(trimethylsilyl)silyl]methane – The First Geminal Di(hypersilyl) Compound with a Central Carbon Atom
Authors: Jeschke Elke , Gross Thoralf , Reinke Helmut , Oehme Hartmut 
Published: July 2007

AbstractMethoxy‐bis[tris(trimethylsilyl)silyl]methane (4), the first compound bearing two hypersilyl groups at a carbon atom, was synthesized by the reaction of tris(trimethylsilyl)silyllithium with dichloromethyl methyl ether. As a byproduct of the reaction, 1,2‐dimethoxy‐1,2‐bis[tris(trimethylsilyl)silyl]‐ethane (5) could be identified. Possible pathways leading to 4 and 5 are discussed. The structure of 4, elucidated by an X‐ray crystal structure analysis, is characterized by tremendous distortions of the molecular skeleton due to the spatial demand of the two extended hemispherical (Me3Si)3Si groups. For example, the central Si–C–Si angle is widened to 132.7°, the trimethylsilyl groups of the two hypersilyl substituents are pressed together to give an average Si–Si–Si angle of 105.6°, and the methoxy carbon atom and the nearest neighboring trimethylsilyl carbon atom approach to a distance of 3.25 Å, i.e. approx. 19% less than the sum of the van der Waals radii of two methyl groups.
Iron‐Mediated Conversions of Eucarvone‐Derived Cationic Dienyl Complexes
Authors: Hirschfelder Andreas , Drost Daniel , Meinhardt Sven , Eilbracht Peter 
Published: July 2007

AbstractCationic cycloheptadienyl iron complexes with new substitution patterns are generated by starting from the eucarvone complex 5 and the analogous triphenyl phosphite complex 6. These complexes are converted with different nucleophiles. Regioselectivity of the nucleophilic attack depends on the substitution pattern of the seven‐membered ring. A new type of cationic system 7b, bearing an alkoxy substituent at C‐1, was treated with nucleophiles leading to the ipso adducts of type 10. Unexpected attack at the central C‐3 of the dienyl moiety is observed during the conversion of cationic complexes of type 9 with nucleophiles. The diene iron complexes, obtained in these reactions, can be converted to substituted cycloheptadienes by oxidative decomplexation, as shown by a selected example.
Novel Inorganic (Carbon‐Free) Chelate Rings: Tris(chelate) Compounds of [N‐(Diphenylphosphinoselenoyl)‐P,P‐diphenylphosphinoselenoic amidato‐Se, Se′] with MIII (M = Sb, Bi, In)
Authors: Cea‐Olivares Raymundo , García‐Montalvo Verónica , Novosad Josef , Woollins J. Derek , Toscano Rubén A. , Espinosa‐Pérez Georgina 
Published: July 2007

AbstractThe [(SePPh2)2N]− ligand 1c forms stable tris(chelates) with the SbIII, BiIII, and InIII ions. The crystal and molecular structures of the resulting compounds 3, 4, and 5 were determined by X‐ray diffractometry. The coordination geometry around the metal centers can be described as a distorted octahedron. This feature and the results obtained by comparing the structures with their sulfur and oxygen analogs lead us to conclude that in both SbIII and BiIII compounds the arrangement around the metals suggests a stereochemically nonactive electron lone pair.
Synthesis and Characterization of Novel Phthalocyanines with Four 16‐Membered Diazadithia Macrocycles
Authors: Yilmaz Ismail , Bekaroǧlu Özer 
Published: July 2007

AbstractMetal phthalocyanines (M = Cu, Ni, Co) 3‐5 bearing four 16‐membered diazadithia macrocycles at the peripheral positions were prepared. Detosylation with concentrated sulfuric acid afforded products containing both sulfonated groups on the aromatic rings of the macrocyclic substituents which are excellently soluble in water and donor sites for binding four CuII ions to give a pentanuclear complex.
Synthesis, Structure and Vibrational Spectra of Ba14InP11
Authors: Carrillo‐Cabrera Wilder , Somer Mehmet , Peters Karl , von Schnering Hans Georg 
Published: July 2007

AbstractBa14InP11 was prepared from the elements in a sealed stainless steel ampoule at 1345 K. The compound is black, brittle and very sensitive to air and moisture. Ba14InP11 crystallises in the tetragonal Ca14AlSb11 type (space group I41/acd, No. 142; a = 17.097 (2) Å, c, = 8, Pearson code tI208). The structure contains isolated P3‐, linear [P3]7‐ and tetrahedral [InP4]9‐ anions. The X‐ray structure analysis and the vibrational spectra show that the [P3]7‐ polyanion is strongly asymmetric with d(P–P) = 2.28 Å and 4.10 Å, corresponding to a [P2]4‐ dumbbell weakly coupled to a single p3‐ anion. The tetraphosphidoindate(III) anion [InP4]9‐ is slightly compressed along the 4 axis, with bond lenght d(In–P) = 2.71 Å. It is shown that the structure is hierarchically related to that of Cu2O, with two interpenetrating frameworks, in which the O and Cu atoms are replaced by condensed [InP4/2] tetrahedron and [BaP4P2/2] octahedra, respectively. Both frameworks are meso configured, containing alternate R and S fragments. The other Ba cations envelop the P6 octahedra and P3 triads forming condensed cubes, tetragonal antiprisms and bicapped trigonal prisms. Therefore, the structure also forms a heterogeneous framework of centred PBa8/2tap tetragonal antiprisms and BaBa8/2cub cubes, consisting of two interpenetrating enantiomorphic nets (R and S) similar to those in the cubic phase RhBi4.
Hydrolysis of Esters and Amides by the Metallo Nucleophile TpCum,MeZn–OH
Authors: Ruf Michael , Vahrenkamp Heinrich 
Published: July 2007

AbstractThe molecular zinc hydroxide complex TpCum,MeZnOH [1, TpCum,Me = tris(3‐cumenyl‐5‐methylpyrazolyl)hydroborate] is a powerful nucleophile. It effects stoichiometric hydrolysis of activated esters RCOOX and amides RCONHX in nonaqueous media. The cleavage products are TpCum,MeZnOCOR and HOX or H2NX, resp. Two of them (TpCum,MeZnOCOCH2‐CH2OH resulting from propiolactone and TpCum,MeZnOCOCF3 resulting from trifluoroacetamide) were characterized by crystal structure determinations.
Palladium‐Catalyzed Reactions in Industry, 4[]. Synthesis of New Palladium Catalysts: First Isolation and Characterization of all Intermediates in a Cyclopalladation Reaction
Authors: Beller Matthias , Riermeier Thomas H. , Haber Steffen , Kleiner Hans‐Jerg , Herrmann Wolfgang A. 
Published: July 2007

AbstractIn order to synthesize chiral palladacycles for stereoselective C–C coupling reactions we studied the cyclopalladation of P‐chiral phosphanes 2 and 3. New palladium complexes of the type L2PdX2 (6, 8) and LXPd–μ‐X2–PdXL (5, 9, X = Cl; L = 2, 3) were isolated. A detailed study of the reactivity of all intermediates towards cyclopalladation proved the mechanism of cyclometalation reactions of o‐tolylphosphanes for the first time. Different deuteration experiments clearly demonstrated the higher reactivity of dimeric palladium complexes towards metalation compared to monomeric species. In agreement with this observation only 5 and 9 gave the cyclopalladated products 4 and 10 as revealed by FAB mass spectrometric investigations. Under the described reaction conditions the synthesis of the corresponding palladacycles 4, 10 is not possible because cyclometalation is a reversible process with LXPd–μ–X2–PdXL as thermodynamic more stable products. The results demonstrate the importance of free coordination sites on the metal atom for cyclometalation reactions or more general CH activation processes.