bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organische Synthesen mit Übergangsmetallkomplexen, 41. Thioenolether durch Insertion von Alkinen in MC‐Bindungen von Thiocarben‐Komplexen und Liganden‐Abspaltung an Kieselgel
Authors: Aumann Rudolf , Schröder Jochen , Heinen Heinrich 
Published: July 2007

Organic Syntheses via Transition Metal Complexes, 41 1. ‐ Thioenol Ethers by Insertion of Alkynes into M = C Bonds of Thiocarbene Complexes and Disengagement of Ligands on Silica GelA first example of reactions between alkynes and thiocarbene complexes is described. Et2NCCCCH3 (2) adds to (alkylthio)phenylcarbene complexes LnMC(SR)C6H5 (1) [LnM = Cr(CO)5. W(WO)5; RCH2CHCH2, CH2C6H5, c‐C6H11, t‐C4H9, C6H5] with insertion of the CC into the MC bond to form stereoselectively [(E)‐β‐(alkylthio)alkenyl]aminocarbene complexes LnMC(NEt2) ‐ C(CH3)C(SR)C6H5 [(E)‐3a–g]. With tungsten, but not with chromium, small amounts of indanone derivatives 4–6 were also obtained. We describe a straightforward and efficient method for the disengagement of ligands from carbene chromium complexes 3 on silica gel. Metal residues remain attached to the solid phase, and products are isolated by elution. Depending on the reaction conditions, different thioenol ethers 7–9 were obtained. Thus (E)‐3a–d on silica gel at ambient temperature under the influence of air give β‐(alkylthio)propenamides OC(NEt2)‐C(CH3)C(SR)C6H5 [(E)‐] and β‐(alkylthio)propenals OCH–C(CH3) = C(SR)C6H5 [(E)‐8]. Thermolysis of 3 on silica gel in the absence of oxygen leads to the formation of aldehydes 8 and 3‐(alkylthio)‐1‐indanones 5. Thermolysis of 3 on silca gel in the presence of sulfur yields β‐(alkylthio)propenethioamides 9 as the only products.
Intramolecular Ene and Related Reactions, 53g). Stereoselective Formation of trans‐1,2‐Disubstituted Cyclopentanes by Intramolecular Cyclisation of Allylsilane Alkylidene 1,3‐Dioxo Compounds
Authors: Tietze Lutz F. , Ruther Michael 
Published: July 2007

AbstractThe alkylidene 1,3‐dioxo compounds 4a–d with an allylsilane moiety undergo a fluoride‐, Lewis acid‐ and TMSOTf‐induced intramolecular cyclisation to give almost exclusively the trans‐1,2‐disubstituted cyclopentanes 5a–d in good to excellent yields. The diastereoselectivity of the reaction was determined as a function of the 1,3‐dioxo moiety and the inductor. The best results were obtained with FeCl3/Al2O3 followed by TMSOTf and Me2AlCl1 the highest selectivity was found in the cyclisation of 4b with TMSOTf leading to 5b and 6b in a ratio of 99.8:0.2. FeCl3/Al2O3 and TMSOTf have not previously been used for this type of reaction. The alkylidene 1,3‐dioxo compounds 4a–d were synthesised by Knoevenagel condensation of the aldehyde 11 with the malonic acid derivatives 11a–d.
(E)‐ und (Z)‐Enole von β‐Ketocarbonsäureamiden
Authors: Wengenroth Horst , Meier Herbert 
Published: July 2007

(E)‐ and (Z)‐Enols of β‐Ketocarboxylic Acid AmidesReaction of dimesitoyldiazomethane (1) with ammonia (3a), primary and secondary amines (3b – o and 3p – v, respectively) leads to the completely enolized amides 4a – v. Besides the chelated Z configuration the unusual E isomer exists in the most cases, too. The Z/E distribution in the equilibrium depends on the steric and electronic effects present in the amide group CONR2R3 and on the solvent.
A Novel Methylenation Method of aldehydes Mediated by Dibutyl Telluride
Authors: Li Sao‐Wei , Huang Yao‐Zeng , Shi Li‐Lan 
Published: July 2007

AbstractIn the presence of dibutyl telluride, (iodomethyl)triphenylphosphonium iodide (1) reacted with aldehydes 2 in THF at 80°C yielding he methylenation products 3 under neutral conditions in good yields.
Facile Diastereoselective Synthesis of 2,6‐Dialkyl‐5‐methylene‐1,3‐dioxan‐4‐ones via α‐Activated Vinyl Esters
Authors: Drewes Siegfried E. , Emslie Neville D. , Karodia Nazira , Khan Abdullah A. 
Published: July 2007

AbstractVinyl esters such as 2, in the presence of DABCO, undergo intial reaction with aldehydes, followed by nucleophilic attack on a second aldehyde molecule. Subsequent intramolecular transesterification affords the dioxanones 5 in high yields and high diastereomeric excesses.
Nonacarbonylbis(μ3‐methylidin)trieisen
Authors: Lentz Dieter , Michael Heike 
Published: July 2007

Nonacarbonylbis(μ3‐methylidyne)triironHalogen exchange reaction in Fe3(CO)9(μ3CF)2 (1) with BBr3 (3) yields Fe3(CO)9(μ3CBr)2 (4), which can be converted by (C4H9)3SnH (5) into Fe3(CO)9(μ3CH)2 (6). 6 is the parent compound of the bis(alkylidyne)triiron clusters. Selective reduction of the CBr moiety in Fe3(CO)9(μ3CBr) (μ3CCO2CH3) (7) results in the formation of Fe3(CO)9(μ3CH) (μ3CCO2CH3) (8). The structure of 8 has been elucidated by an X‐ray crystalstructure determination.
Nickel(0)‐katalysierte Kupplung von (Tricyclo[4.1.0.02,7]hept‐1‐yl)‐magnesiumbromid und verwandten Grignard‐Verbindungen mit Aryl‐, Vinyl‐ und Alkinylhalogeniden
Authors: Kottirsch Georg , Szeimies Günter 
Published: July 2007

Nickel(0)‐Catalyzed Cross Coupling Reactions of (Tricyclo[4.1.0.02,7]hept‐1‐yl)magnesium Bromide and Related Grignard Reagents with Aryl, Vinyl, and Alkynyl Halides(Tricyclo[4.1.0.02,7]hept‐1‐yl)magnesium bromide (1c) and similar Grignard reagents like 2c, 3a–d, and 4 were cross‐coupled with a series of aryl, vinyl, and alkynyl chlorides or bromides in the presence of approximately 1% of [1,2‐bis(diphenyl‐phosphino)ethane]nickel dichloride (NidppeCl2) leading to bridgehead‐substituted aryl‐, vinyl‐, and alkynylbicyclo[1.1.0]‐butanes in varying yields.
Metal ion binding by amino acids: Strontium and barium l‐aspartate trihydrate Sr/Ba(l‐Asp) · 3 H2O
Authors: Schmidbaur Hubert , Mikulik Patrizia , Müller Gerhard 
Published: July 2007

AbstractStrontium and barium l‐aspartate are obtained by neutralization of aqueous solutions of l‐aspartic acid with strontium or barium hydroxide, respectively. Slow crystallization from hot water affords the crystalline trihydrates, saturated solutions of which show pH values of 11.0 and 10.8 at ambient temperature. – The crystal structure of the two compounds has been determined by single crystal X‐ray diffraction. The compounds are isomorphous (orthorhombic, space group P212121), and the structural parameters are very similar as expected from the small differences in the ionic radii of the two metals. – The cations are arranged in double strings parallel to the b axis. The l‐aspartate dianions are bridging these double strings by chelating contacts of the two carboxylate groups with the metal atoms of different strings to give layers. While the α‐carboxylate groups are only bidentate and associated with one metal atom each, the β‐carboxylate oxygen atoms are also each bridging two adjacent metals of the neighbouring string. The three water molecules are all coordinated to the metal atoms, which attain coordination number 9. The amino groups are not engaged in metal coordination, but are part of a system of hydrogen bonds cross‐linking the layers.
Über Metallalkyl‐ und ‐aryl‐Verbindungen, 44 Darstellung und Struktur von Methylnatrium. Strukturbestimmung an NaCD3‐Pulvern bei 1.5 und 300 K durch Neutronen‐ und Synchrotronstrahlenbeugung
Authors: Weiss Erwin , Corbelin Siegfried , Cockcroft Jeremy Karl , Fitch Andrew Nicholas 
Published: July 2007

Metal Alkyl and Aryl Compounds, 441) – Preparation and Structure of Methylsodium. Structure Determination using NaCD, Powders at 1.5 and 300 K by Neutron and Synchrotron Radiation Diffraction[D3]Methylsodium (NaCD3) has been obtained by the reaction of [D3]methyllithium with sodium tert‐butoxide. Its crystal structure has been determined from NaCD3 powder samples using the combination of neutron and synchrotron radiation diffraction techniques. Studies at 1.5 and 300 K show a new structure type (orthorhombic, space group I222, Z16). Na and C atomic positions have been obtained from synchrotron radiation data and subsequently D positions by neutron diffraction. The complete structure has been refined using Rietveld methods. – Half of the ions are arranged in tetramers, (NaCD3)4, similar to those in methyllithium. The orientation of the methanide ions with respect to the three next Na ions is staggered. The remaining 8 Na and 8 methanide ions interconnect the tetramers by Na‐C contacts; their Na ions are arranged in zigzag chains. Thus, the structure of methylsodium shows elements of the methyllithium and methylpotassium structure. All methanide ions are trigonal‐pyramidal with C‐D 109 pm and D‐C‐D angles of 106° (1.5 K). Na‐C distances vary from 253 to 291 pm, depending upon the methyl‐Na orientation. IR data of NaCD3 are given.
N‐Aryl‐O‐(α‐aminoacyl)hydroxylamine: Modellreaktionen zur Aktivierung von monocyclischen aromatischen Aminen zu ultimaten Carcinogenen durch α‐Aminosäuren
Authors: Meier Chris , Boche Gernot 
Published: July 2007

N‐Aryl‐O‐(α‐aminoacyl)hydroxylamines: Model Reactions for the Activation of Monocyclic Aromatic Amines into Ultimate Carcinogens with α‐Amino AcidsThe rearrangement of the new α‐aminohydroxamic acids 15 and 18 to the likewise new N‐(α‐aminoacyloxy)arylamines [“N‐(acyloxy)arylamines”] 19 and 20, respectively, is observed in amine‐catalyzed model reactions. N‐(acyloxy)arylamines such as 19 and 20 are indicated to be ultimate carcinogens of aromatic amines which are able to react with bionucleophiles such as the DNA bases. The formation of 19 and 20 was proven by trapping these reactive intermediates with the model nucleophile N‐methylaniline (21) to give the hydrazines 22 and‐depending on the substitutent in 19 and 20‐the so‐called ortho amination products 23. Analogous reactions of the aceto‐and pivalohydroxamic acids 24 and 25 lead also to the adducts 22 and 23, respectively, in comparable yields. These results demonstrate that the O‐α‐aminoacylation as shown here may be similarily used in model reactions for the activation of carcinogenic aromatic amines as the O‐acetylation.
Untersuchungen zur Chemie von Isoindolen und Isoindoleninen, XXXVII. Symmetrisch substituierte 2‐Alkyl‐2H‐isoindole
Authors: Kreher Richard P. , Sewarte‐Roß Günter , Vogt Günther 
Published: July 2007

Studies on the Chemistry of Isoindoles and Isoindolenines, XXXVII1) – Symmetrically Substituted 2‐Alkyl‐2H‐isoindoles2‐Alkyl‐Rn‐2H‐isoindoles (1; Rn=4,5,6,7‐tetramethyl, 4,5,6,7‐tetrachloro) have been prepared efficiently by the N‐oxide route and characterized by spectroscopic means.
Cyclopentenyliden‐Komplexe aus Alkinylcarben‐Komplexen, Lithiumaryl und H+
Authors: Fischer Helmut , Meisner Thomas , Hofmann Josef 
Published: July 2007

Cyclopentenylidene Complexes from Alkinylcarbene Complexes, Aryllithium and H+[Alkoxy(phenylethynyl)carbene]pentacarbonyl complexes of chromium and tungsten, (CO)5M[C(CCPh)OR] (1) (M  Cr, W, R  Me, Et) react with Li[C6H4R′‐p] (R′  H, Me) and HBF4 ‐ Et2O to give the vinylcarbene complexes (CO)5‐M{C[CHC(Ph)C6H4R′‐p]OR} 2 and two isomeric cyclopentenylidene complexes 3 and 4. The cyclopentenylidene ligand is formed from two carbene ligands of 1, [C6H4R′‐p]− and H+. The structure of 4a (M  W, R  Et, R′  Me) is established by an X‐ray structure analysis. The product ratio strongly depends on the reaction conditions. The complex 3c (M  Cr, R  R′  Me) reacts with ethyl vinyl ether to give the 3,5‐bis(methylene)cyclopentene derivative 8 by metathesis.
Preparation of donor‐acceptor‐substituted vinylcyclobutanes
Authors: Gruseck Ursula , Heuschmann Manfred 
Published: July 2007

Abstract2‐Methylen‐1,3‐dioxolane (1) and the methyl acrylates or crotonates 2 form [2+2] cycloadducts 3 which are reduced to give alcohols 6. Oxidation of these alcohols at low temperatures leads to unstable aldehydes 7, which either rearrange to dihydropyrans 5 or react with Wittig(‐Horner) reagents to afford donor‐acceptor‐substituted vinylcyclobutanes 8. The cis‐vinylcyclobutane 8g is prepared by [2+2] cycloaddition of dioxolane 1 and methyl (2E,4Z)‐hexadienoate (9). The configurations and preferred conformations of the vinylcyclobutanes 8 have unequivocally been assigned on the basis of 13C‐and 1H‐NMR spectra.
Vinylcyclobutane‐cyclohexane rearrangements: zwitterions as discrete intermediates
Authors: Gruseck Ursula , Heuschmann Manfred 
Published: July 2007

AbstractDonor‐acceptor‐substituted vinylcyclobutanes 1 rearrange to cyclohexenes 2 at temperatures between 20 and 195°C. In solvents of low polarity, [2+2] cycloreversion competes with ring enlargement. Under acidic conditions, addition of nucleophiles to vinylcyclobutanes 1 with ring opening is observed. Stereospecificity of rearrangement and [2+2] cycloreversion are functions of temperature, solvent polarity and acid catalysis. Strong dependence on solvent polarity is found for the rates of both reactions. The mechanisms of the thermally induced and acid‐catalyzed reactions are discussed on the basis of stereospecificity, kinetic parameters and trapping of intermediates. Two structurally different zwitterions 13 and 14 are proposed as intermediates, one of which is responsible for rearrangement, the other for diastereomerization and [2+2] cycloreversion.
Röntgenstrukturanalyse des dimeren 2,2‐Diphenylcyclopropanthiocarbonsäure‐S‐tert‐butylester‐Lithium‐Enolat · TMEDA‐Komplexes: ein „ganz normales”︁ Ester‐Enolat und ein „ganz normales”︁ Methylencyclopropan‐Derivat
Authors: Hahn Ekkehardt , Maetzke Thomas , Plattner Dietmar A. , Seebach Dieter 
Published: July 2007

X‐ray Crystal Structure of the Dimeric tert‐Butyl 2,2‐Diphenylcyclopropanecarbothioate Lithium Enolate · TMEDA Complex: an “Ordinary” Ester Enolate Containing an “Ordinary” Methylenecyclopropane MoietyAfter many unsuccessful attempts we now succeded in growing a suitable crystal of a cyclopropanecarbothioate lithium enolate (title compound 11c) for X‐ray crystal structure analysis. 11c crystallizes as a tetramethylethylenediamine (TMEDA) complex in large cubes and contains hexane, is unstable above − 20°C and twinned. 11c is not C‐lithiated, but exhibits features normal for an ester lithium enolate: a double bond with planar trigonal centers, a methylene cyclopropane moiety with bond lengths and angles almost identical with those in corresponding hydrocarbons, a dimeric aggregation with an almost planar Li‐O‐Li‐O ring, with the large hydrocarbon units in a cis arrangement (Figure 1,2). A comparison with other lithiated cyclopropanes is made (Figure 3). The X‐ray crystal structure analysis shows 11c to form a channel structure in which n‐hexane is included. The structure described here is the first one of a thiocarboxylic acid S‐ester lithium enolate.
Unerwartete Diels‐Alder‐ und Oxidations‐Reaktionen von Benzo[c]thiophenen
Authors: Volz Wolfgang , Voß Jürgen , Adiwidjaja Gunadi 
Published: July 2007

Unexpected Diels‐Alder and Oxidation Reactions of Benzo[c]thiophenesThe oxidation of thiophenes by peracids to form thiophene S‐oxides could not be carried out with benzo[c]thiophenes. With the sterically hindered compound 1a the quinones 2 and 3 were produced whereas the anisyl‐substituted derivative 1b formed the sulfine 5. Significantly different behaviour of 1a and 1b was also observed for the Diels‐Alder reaction with N‐phenylmaleimide. The unexpected and unusual adduct 6 was the only product formed from 1a, with low yield though, whereas the normal Diels‐Alder adduct was obtained from 1b.
Dimethyldioxirane epoxidation of β‐oxo enol ethers
Authors: Adam Waldemar , Hadjiarapoglou Lazaros 
Published: July 2007

AbstractThe synthesis of the epoxides 2a–f by epoxidation of the β‐oxo enol ethers 2,2‐dimethyl‐3(2H)‐furanone (1a), (Z)‐2(ethoxymethylene)cyclohexanone (1b), and 3‐alkoxy‐5,5‐dimethyl‐2‐cyclohexenones 1c–f with dimethyldioxirane is reported. These labile epoxides (stable below 0°C) were isolated and characterized spectroscopically (IR, 1H, and 13C NMR). Warming up to room temperature led to decomposition to afford complex product mixtures. When the epoxidation of 3‐ethoxy‐5,5‐dimethyl‐2‐cyclohexenone (1c) was conducted above 0°C, the epoxide 2c afforded the rearrangement product 3‐ethoxy‐2‐hydroxy‐5,5‐dimethyl‐2‐cyclohexenone (3).
Organobor‐Schwefel‐Verbindungen mit Bicyclo[x.3.0]alk‐3‐en‐Struktur — Herstellung und Charakterisierung
Authors: Köster Roland , Seidel Günter , Boese Roland 
Published: July 2007

Organoboron‐Sulfur Compounds with Bicyclo[x.3.0]alk‐3‐ene Structure — Preparation and CharacterisationThe compounds (R  CH3: I: R  C6H5: II) are prepared from (E)ClSi(CH3)2C(R3)C(C2H5)B(C2H5)Cl [R3  CH3; A; R3  C(CH3)CH2: B] with LISR. ‐ A and B react with LiS(CH2)nSLi (n = 2: Li2‐1; n = 3: Li2‐2 n = 4: Li2‐3) to form the bicyclic compounds R3)C(C2H5)B
Cyclopropan‐Derivate, 2. Selbst‐Acylierung der α‐Alkyl‐γ‐lactone zu Herstellung von Bis(1‐alkylcyclopropyl)ketonen über Spiro[4.4]acetale
Authors: Böhrer Gerald , Knorr Rudolf , Böhrer Petra 
Published: July 2007

Cyclopropane Derivatives, 2. — Self‐Acylation of α‐Alkyl‐γ‐lactones To Give Bis(1‐alkylcyclopropyl)ketones via Spiro[4.4]acetalsHigh‐yield synthetic ways are recommended for the title lactones 1.The coupling of two 2‐alkyl‐4‐butanolides is possible in an inter‐(1b, c) or intramolecular fashion (4c) to give spiro[4.4] acetals 8 or 9 respectively, in the absence of hindering substituents. Symmetrically substituted bis(1‐alkylcyclopropyl)ketones 12 and 13 may be prepared by acidic cleavage of those spiro[4.4] acetals lacking 2,7‐substituent.
Cyclopropan‐Derivate, 3. (1‐Alkylcyclopropyl)ketone durch Acylierung von α‐substituierten γ‐Lactonen
Authors: Böhrer Gerald , Böhrer Petra , Knorr Rudolf 
Published: July 2007

Cyclopropane Derivatives, 3. — (1‐Alkylcyclopropyl)ketones by Acylation of α‐Substituted γ‐LactonesThe 2‐acylation of 2‐substituted 4‐butanolides 2 is moderately sensitive to steric crowding, whereas the subsequent ring‐ opening of 2‐acyl‐2‐alkyl‐4‐butanolides 4, 11 to give‐chloro ketones 6, 12 by chloride‐transferring acid derivatives be‐comes difficult with bigger lactone substituents. Similar observations pertain to the preparation of y‐chlorobutanoyl chlorides 10 from 2‐alkyl‐4‐butanolides 2. The proper choice of the starting 4‐butanolides (2a, b or 14 but not 2c) provides for an indirect coupling of two different lactones to y,y‐dichloro ke‐tones 12. Dicyclopropyl ketones 13 with variable patterns of substitution may thus be prepared from 4‐butanolides in a direct manner with global yields exceeding 50% and without purification of intermediate products (except for acid chlorides like 10).
Beiträge zur Chemie der Halogensilan‐Addukte, 21. Darstellung, Eigenschaften, Kristall‐ und Molekülstruktur von Dichloro(1,10‐phenanthrolin)bis(trichlorsilyl)silicium, (SiCl3)2SiCl2 · phen
Authors: Kummer Dieter , Chaudhry Subhash C. , Depmeier Wulf , Mattern Günter 
Published: July 2007

Contributions to the Chemistry of Halogenosilane Adducts, 21. — Preparation, Properties, Crystal and Molecular Structure of Dichloro(1,10‐phenanthroline)bis(trichlorosilyl)silicon, (SiCl3)2SiCl2 · phenSi3Cl8 · phen (1) is obtained as a stable solid by the reaction of Si3Cl8 with phen. The structure of 1 in solution and its reactions correspond to that of Si3Cl8 · bipy reported earlier (1H‐NMR and IR studies). Rearrangement of 1 occurs in solution to give bis(silyl)‐substituted 1,2‐dihydrophenanthroline. From THF/C6H6 solution crystalline Si3Cl8 · phen · C6H6 (1a) is obtained. The X‐ray structure determination shows 1a to be monoclinic, space group P21/n (Z = 4). Phenanthroline is coordinated to the central silicon atom of the trisilane with its plane normal to the linear Si3 chain having two tetrahedral terminal SiCl3 groups. The coordination octahedron is regular.
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXXVIII. Synthese, Eigenschaften und fluktuierendes Verhalten von (Ether‐Phosphan)palladium‐Komplexen
Authors: Lindner Ekkehard , Speidel Robert , Fawzi Riad , Hiller Wolfgang 
Published: July 2007

Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XXVIII. — Synthesis, Properties and Fluxional Behavior of (Ether‐Phosphine)palladium ComplexesCl2Pd(COD) (1) (COD = 1,5‐cyclooctadiene) reacts with 1 equiv, of the (ether‐phosphine) ligand Ph2P∼D (2a–c) (D = CH2C4H7O (a), CH2C4H7O2 (b), CH2CH2OCH3 (c)] to give the dimeric complexes [μ‐ClPdCl(Ph2P∼D)]2 (3a–c) (P∼D = η1‐P‐coordinated). According to the field‐desorption mass spectra which show only one peak for the monomeric moieties ClPd(Ph2P∼D), 3a–c have a very weak Pd2Cl2 bridge. trans‐Cl2Pd(Ph2P∼D)2 (4a–c) is obtained either from 3a–c and 2a–c by cleaving the Pd2Cl2 bridge or from 1 and 2 equiv. of the ligands 2a–c. 4c crystallizes in the monoclinic space group P21/c with Z = 2. AgClO4 selectively abstracts one Cl⊖ ligand from 4a–c which results in the formation of the cationic complexes [trans‐(Ph2P∩D)(Ph2P∼D)PdCl]⊕ (5a–c) (P∩D = η2‐D,P‐coordinated) containing one chelated and one η11‐P‐bonded (ether‐phosphine) ligand. 5a–c show fluxional behavior which is demonstrated by temperature‐dependent 31P{1H}‐NMR investigations. The coalescence points have been determined and are at 253 (5a), 303 (5b), and 283 K (5c). The activation enthalpies ΔG‡ are estimated at 48, 58, and 54 kJ/mol. The abstraction of the second Cl⊖ ligand from 5a–c succeeds only in the presence of AgSbF6 yielding the dicationic bis(chelate) complexes [trans‐(Ph2P∩D)2Pd]2⊕ (6a–c). The latter are also obtained from 4a–c) and AgSbF6. The hydrogenating properties of 3a–c and 4a–c toward 1‐hexyne are investigated in comparison with trans‐Cl2Pd(Ph2P‐CH2CH2CH3)2.
Cyclic dinuclear gold(I) complexes: The crystal structure of bis‐μ‐[(diphenylphosphino)(diphenylphosphinoselenoyl)methane]‐digold(I) bis(perchlorate)
Authors: Schmidbaur Hubert , Eschenbach Jennifer Ebner Von , Kumberger Otto , Müller Gerhard 
Published: July 2007

Abstract[(CO)AuCl] reacts with equimolar amounts of Ph2PCH2P(Se)Ph2 (dpmSe) to afford ClAuPh2PCH2P(Se)Ph2, in which dpmSe is bound to gold in a monodentate fashion by phosphorus. Subsequent reaction of this 1:1 complex with AgClO4 results in the formation of the 10‐membered ring complex 4 which crystallizes in the monoclinic space group P21/n with approximately centrosymmetric dicationic units, in which two gold (I) atoms are doubly bridged by two dpmSe ligands coordinated by phosphorus and selenium. The coordination at the gold atoms deviates from linearity and implies an Au···Au interaction with the gold(I) atoms separated by a distance of 3.020(1) Å.
Isomere Aminoborane und Amin‐Borane mitcis‐BC  CSi‐Gruppierung — Herstellung und Charakterisierung
Authors: Könter Roland , Seidel Günter , Wrackmeyer Bernd 
Published: July 2007

Isomeric Aminoboranes and Amine‐Boranes with cis‐BC  CSi Groupings — Preparation and CharacterisationThe reaction of the heterocycles ) [R3  CH3: A; R3  C(CH3): CH2: B] with the prim.‐aminohydroxyalkanes H2NROH [R  CH2CH2: 1; CH(C2H5)CH2: rac‐2, R‐2,; [CH2]3 : 3;  [CH2]4 : 4], the prim‐aminophenols H2NC6H4OH [ortho; 5; meta: 6], and the sec.‐aminohydroxyalkanes HN(CH3)  ROH [R  [CH2]2: 7; (R,S)‐CH(CH3)CH(C6H5) : 8; (S,S)‐CH(CH)3)CH(C6H5): 9] leads to elimination of CH3NH2 with formation of the compounds 11a, b, 12–15 and 17–19 as monocyclic aminoboranes B(C2H5) (R1  H, CH3; R3  CH3) and iso‐11a,b, iso‐12‐iso‐15 as bicyclic amine‐boranes . The isomeric compounds 11a and iso‐11a are transformed into one another by crystallisation and by dissolution or distillation, resp. A reacts with the tert.‐aminoethanol (CH3)2NCH2CH2OH (10) to give the acyclic compound (CH3)2N(CH2)2OSi(CH3)2C(CH3  C(C2H5)B(C2H5)O(CH2)2‐N(CH3)2 (20). Further reactions of A with the NH2 compounds HN(CH3)[CH2]2NH2 (21), CH3C(O)NH2, and NCNH2 to the compounds E, 23, and 24, resp., are described. — The compounds (i1) and cis‐HC(C2H5)  C(CH3)Si(CH3)2ORNH2 (i2) are formed as side products by BC(vinyl) fission.