bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Characterization of β‐Phosphaenones An Investigation on the Conjugative Properties of the PC Bond
Authors: Sluis Marcel Van Der , Bickelhaupt Friedrich , Veldman Nora , Kooijman Huub , Spek Anthony L. , Eisfeld Wolfgang , Regitz Manfred 
Published: July 2007

AbstractThermally and air‐stable β‐phosphaenones were synthesized by functionalization of Mes*PCCl2 (1; Mes* = supermesityl = 2,4,6‐tri‐tert‐butylphenyl). At low temperature, 1 was lithiated by halogen‐metal exchange with n‐butyllithium to give the phosphanylidene carbenoid (Z)‐Mes*PC(Cl)Li [(Z)‐2] which reacted with acid chlorides to furnish the C‐carbonyl‐substituted phosphaalkenes (Z)‐Mes*PC(Cl)R (3: P = COtBu; 4: R = COPh; 5: R = COOEt). The reaction of (Z)‐2 with carbon dioxide furnished the carboxylate 6, which was converted by treatment with pivaloyl chloride or trimethylsilyl chloride into the phosphaalkenes 7 and 8 functionalized at the carbon atom by an anhydride or a trimethylsilyl ester function, respectively. Acidification of 6 or hydrolysis of 8 with water in chloroform solution afforded the novel carboxylic acid (Z)‐Mes*PC(Cl)COOH (9). Spectroscopic investigations (NMR, UV, IR) of 3–9 and the X‐ray structures of 3 and 4 are presented. Based on these properties and on theoretical calculations, the occurrence of conjugation in the β‐phosphaenone system is discussed and compared with the well‐known conjugation in normal enones.
Synthesis of Bis(trichloromethyl)tetra‐ and ‐heptasulfane from Titanocene Polysulfide Complexes and Structure of (CCl3)2S7
Authors: Steudel Ralf , Pridöhl Markus , Buschmann Jürgen , Luger Peter 
Published: July 2007

AbstractCCl3SCl reacts with (C5H5)2TiS5 to give the heptasulfane (CCl3)2S7 which forms colorless crystals of m.p. 38°C. An X‐ray structural analysis revealed that the C‐S7‐C chain is helical but the CCl3 groups are slightly tilted. In the triclinic crystals the molecules are arranged parallel to each other. Decomposition of (CCl3)2S7 provides other members of the homologous series with 4–12 sulfur atoms as shown by HPLC analysis. The reaction of CCl3SCl with (C5H4‐CH3)4Ti2S4 yields colorless crystals of (CCl3)2S4, demonstrating the usefulness also of dinuclear titanocene polysulfide complexes for the synthesis of organic polysulfanes. Infrared, Raman, and 13C‐NMR spectra of (CCl3)2S7 and (CCl3)S7 are reported.
Electronic Structure of Planar‐Tricoordinated Phosphorus in Titanium‐Boron Complexes
Authors: Gleiter Rolf , Silverio Sandro Johannes , Binger Paul , Sandmeyer Frank , Erker Gerhard 
Published: July 2007

AbstractThe electronic structure of the recently synthesized complex 5 obtained by the reaction of Cp2Ti(PMe3)(tBu‐CP) with (Et2BH)2 was analyzed by means of molecular orbital (MO) calculations. The methods applied were the extended Hückel and the ab initio Hartree‐Fock procedures. The highest occupied MOs were derived from molecular fragments. The geometrical parameters calculated for a simplified model (6) are close to those obtained from an X‐ray investigation of 5. The analysis of the results shows a strong donor‐acceptor interaction between the P‐B ó bond and the Ti center. The phosphorus lone pair is not involved in bonding.
Substituted Variants of the Cluster Type Fe3(CO)9(μ3‐η2‐RCN)
Authors: Suter Pierre , Vahrenkamp Heinrich 
Published: July 2007

AbstractVarious aromatic nitriles were used for the preparation of the nitrile‐capped clusters Fe3(CO)9(μ3‐η2‐RCN) (2) by reaction with Fe3(CO)12 under hydrogen. Electron‐rich nitriles decrease, electron‐poor nitriles increase the thermal stability of clusters 2. With CN‐substituted pyridines only traces of clusters 2 could be obtained. CO replacement in Fe3(CO)9(PhCN) (2a) by isonitriles also causes a lowering of the stability. Conversely, more stable products were obtained by substitution reaction with trimethyl phosphite. One PPh3 and two dppm derivatives were also obtained. The structure of Fe3(CO)8‐P(OMe)3(μ3‐η2‐PhCN) (5a) was determined.
Stereoselective Substitution at Phenyl‐Substituted γ‐Lactols with Organometallic Compounds
Authors: Schmitt Andreas , Reißig Hans‐Ulrich 
Published: July 2007

AbstractA variety of monosubstituted γ‐lactols 4–6 were prepared in good yields by DIBAL reduction of the corresponding γ‐lactones 1–3. The monophenyl‐substituted lactols 4b–6b were transformed into disubstituted tetrahydrofuran derivatives by replacement of the hydroxyl group by the alkyl residue of organometallic compounds used as nucleophiles. The diastereoselectivity of the substitution was found to depend strongly on the substitution pattern of the γ‐lactols. For the reaction of the 3‐ and 4‐substituted derivatives 4b and 5b, respectively, good to excellent trans selectivity was observed, while the 5‐substituted derivative reacted without any diastereoselectivity. These results were interpreted by means of the Felkin‐Anh model.
Synthesis and Structure of a Cyclic Complex of Digold Sulfide Au2S and of Related Compounds
Authors: Hofreiter Stefan , Paul Martin , Schmidbaur Hubert 
Published: July 2007

Abstract1,4‐Bis(diphenylphosphanylmethyl)benzene (1) was converted into its bis[chlorogold(I)] complex [1 · (AuCl)2] upon treatment with two equivalents of chloro(dimethyl sulfide)‐gold(I). The reaction of 1 · (AuCl)2 with one equivalent of silver tetrafluoroborate afforded a cyclic di[gold(I)]chloronium tetrafluoroborate [1 · Au2Cl+ BF‐4]. Substitution of chloride in 1 · (AuCl)2 by sodium methanethiolate in wet chloroform, gave the bis[methylthiogold(I)] complex 1 · (AuSMe)2], while with sodium sulfide a cyclic complex 1 · Au2S was obtained. Reaction of 1 · (AuCl)2 with two equivalents of AgBF4 followed by treatment with diphenyldisulfide or sodium methanethiolate yielded the cyclic methyl/phenylsulfonium tetrafluoroborates 1 · Au2SPh+ BF‐4 and 1 · Au2SMe+BF‐4, respectively. All compounds were identified on the basis of their analytical and spectroscopic data. The crystal structures of 1 · (AuCl)2, 1 · (AuSMe)2, and 1 · Au2S have been determined. The Au2S complex has a cyclic structure with a narrow Au‐S‐Au angle of 86.7(1)° indicating a significant intraannular Au…Au interaction.
Organometallic Aqua Complexes, III. Olefin Aqua Complexes of Rhodium(I)
Authors: Kölle Ulrich , Görissen Ralf , Wagner Trixie 
Published: July 2007

AbstractDehalogenation of halide precursors [(olefin)RhCl]2 [olefin = ethylene, 1,5‐cyclooctadiene (COD], norbornadiene (NBD), 2,3‐dimethylbutadiene (DMB)] in water gave the respective cis‐diolefin aqua ions, characterized by NMR spectroscopy in solution. Attempted isolation of the tosylate salt [(COD)Rh‐(H2O)2]OTs yielded crystals of (COD)Rh(H2O)(η1‐OTs) characterized by X‐ray structural analysis. [(NBD]Rh(H2O)2]SbF6 in the presence of adventitious toluene decomposed into [(NBD])Rh(η6‐toluene)]SbF6 and [(NBD]2Rh]SbF6, both complexes were isolated and structurally characterized. Ethylene exchange in [(C2H4)2Rh(H2O)2]+ is fast with k2 of the order of 104–105 s‐1 · M‐1. The rate constant for water exchange in [CODRh(H2O)2]+ is estimated as 104 s‐1 (ΔDLG ≈︁ 25 kJ/mol) at 173 K.
A Molybdenum‐Catalysed Electrocyclisation‐Cycloaddition Sequence: Synthesis and Structure of a Pentacyclic Unsaturated Ketone
Authors: Schmidt Thomas , Lutz Frank 
Published: July 2007

AbstractThe pentacyclic unsaturated ketone 3 is obtained as the sole product by the reaction of pinocarvone (1) with cycloocta‐triene in the presence of catalytic amounts of dicarbonyl‐bis(η4‐pinocarvone)molybdenum (2). Compound 3 formally resulting from a [4 + 2] cycloaddition reaction of bicy‐clo[4.2.0]octa‐2,4‐diene with the alkene fragment of pinocarvone was characterised by means of spectroscopy (1H, 13CNMR, IR, MS) as well as by X‐ray crystal structure analysis. A mechanism is proposed involving rigid molybdenum complexes as intermediates in order to explain the stereospecificity of the reaction.
Controlled Conversion of the Transient 2‐Mesityl‐1,1‐bis(trimethylsilyl)silene into a Tetrahydro‐2,3‐disilanaphthalene, a 1,2‐Disilacyclobutane, or a 1,3‐Disilacyclobutane
Authors: Krempner Clemens , Reinke Helmut , Oehme Hartmut 
Published: July 2007

AbstractMesityl[tris(trimethylsilyl)silyl]methanol (1) reacts with strong bases with elimination of trimethylsilanolate according to a Peterson‐type mechanism, the outcome of the reaction being dependent on solvent, temperature, and nature of the organometallic base applied. Thus, 1 was converted by treatment with MeLi in ether at –78°C to (E)‐1,2,3,8a‐tetra ‐hydro‐1‐mesityl‐5,7,8a‐trimethyl‐2,2,3,3‐tetrakis (trimethylsi‐lyl)‐2,3‐disilanaphthalene (3), formally a [2 + 4] cyclodimer of the transient silene (Me3Si)2Si=CHMes (2). The reaction of 1 with PhMgBr in THF after some days resulted in the formation of (Z)‐3,4‐dimesityl‐1,1,2,2‐tetrakis(trimethylsilyl) ‐1,2‐disilacyclobutane (6) as the main product besides small quantities of 3, the polysilane (Me3SiSi(SiMe3)2CH2Mes (10), and the alkoxysilane (Me3Si)3SiCH(Mes)OSi(Si‐Me3)2CH2Mes (7). Compound 6, the formal [2 + 2] cycloadduct of 2, can also be obtained by thermal treatment of 3 and is considered to be the thermodynamically more stable silene dimer whereas 3 is the kinetically preferred product. At high LiBr concentrations in the reaction mixture 1 was converted by PhMgBr in THF to (E)‐2,4‐dimesityl‐1,1,3,3‐tetrakis(tri‐ methylsilyl)‐1,3‐disilacyclobutane (13) besides 6 and [bis(tri‐methylsilyl)silyl]mesityl(trimethylsiloxy)methane (11). The unforeseen formation of 13 is discussed as proceeding via the silene‐lithium bromide adduct (Me3Si)2Si(Br)CH(Li)Mes (12). In the absence of LiBr 1 was converted by MeLi in THF at –78°C to 11 and the trisilane (Me3Si)2Si(Me)CH2Mes (4b). Probable pathways of the formation of all new compounds are discussed. For 6 and 13 the results of the X‐ray structural analyses are given.
Synthesis and Reactivity of Silicon Transition Metal Complexes, 34. Pentachlordisilanyl‐ und Disilanyl‐Komplexe von Molybdän und Wolfram: Darstellung, Struktur und spektroskopische Charakterisierung
Authors: Malisch Wolfgang , Lankat Reiner , Seelbach Wolfgang , Reising Joachim , Noltemeyer Mathias , Pikl Ralf , Posset Uwe , Kiefer Wolfgang 
Published: July 2007

Synthesis and Reactivity of Silicon Transition Metal Complexes, 34[*]. — Pentachlorodisilanyl and Disilanyl Complexes of Molybdenum and Tungsten: Synthesis, Structure, and Spectroscopic CharacterizationReaction of the lithium metallates Li[M(PMe3)(CO)2C5R5] [M = Mo, W; R = H (1a, b), Me (1c, d)] with Si2Cl6 (2) leads to the formation of the pentachloro(metallo)disilanes 5R5(OC)2(Me3P)M—SiCl2—SiCl3 (3a—d), which are transformed into the metallo disilanes C5R5(OC)2(Me3P)M—SiH2—SiH3 (4a—d) on treatment with LiAlH4. The disilanes 4a—d are reconverted into 3a—d in the presence of tetrachloromethane. Extensive spectroscopic investigations (NMR, Raman, and IR spectroscopy) were performed to establish the transition‐metal effect especially with respect to the H5Si2 ligand. The molecular structure of C5Me5(OC)2(Me3P)W—SiCl2—SiCl3 (3d) was determined by single‐crystal X‐ray diffraction.
Synthesis and Reactivity of Silicon Transition Metal Complexes, 33. Metallo Silanols and Metallo Siloxanes, 8. Metallo‐silanole vom Typ C5R5(OC)2(Me3P)M—SiPh2OH (M = Cr, Mo, W): Darstellung nach der Dimethyldioxiran‐Methode und Überführung in funktionalisierte Metallo‐disiloxane
Authors: Malisch Wolfgang , Schmitzer Siegfried , Lankat Reiner , Neumayer Michael , Prechtl Frank , Adam Waldemar 
Published: July 2007

Synthesis and Reactivity of Silicon Transition Metal Complexes, 3332. Mitteilung: Lit.

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— Metallo Silanols and Metallo Siloxanes, 8

7. Mitteilung: Lit.

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— Metallo Silanols of the Type C5R5(OC)2(Me3P)M‐SiPh2OH (M = Cr, Mo, W): Preparation According to the Dimethyldioxirane Route and Conversion into Metallo Disiloxanes

Herrn Professor Max Schmidt zum 70. Geburtstag gewidmet.
The metallo silanes C5R5(OC)2(Me3P)M‐SiPh2H (4a‐c), are converted into the corresponding metallo silanols C5R5(OC)2‐(Me3P)M‐SiPh2OH [R = H, M = Cr (6a); R = Me, M = Mo (6b); M = W (6c)] by oxofunctionalization with dimethyldioxirane (5). Treatment of 6b, c with the chlorosilanes Me2Si(R)Cl [R = H (3b), [R = Cl (3c)] in the presence of triethylamine gives access to the metallo disiloxanes C5Me5(OC)2(Me3P)M‐SiPh2OSiMe2R (M = Mo, R = H (7a); M = W, R = Cl (7b)]. The structure of tungsten silanol 6c is determined by X‐ray diffraction analysis.
P8 and P12 as Complex Ligands
Authors: Scherer Otto J. , Berg Gerald , Wolmershäuser Gotthelf 
Published: July 2007

AbstractThe thermal and/or photochemical reaction of [Cp‴Co(CO)2] (1), Cp‴ = 1,2,4‐tBu3C5H2, with white phosphorus, P4, gives besides [(Cp‴Co)2 (P2)2] (2) the trinuclear complexes [(Cp‴Co)3P8] (3) and [(Cp‴Co)3P12] (4), the Pn ligands of which form P5–P3 and P5–P7 skeletons, structural motifs, which formally can be derived from Hittorf's phosphorus. The X‐ray crystal structure analysis of 3 confirmed its P5–P3 framework.
Komplexe von Halogenid‐Ionen mit 1‐Halogen‐2‐phenylacetylenen. Kristallstrukturen von PPh4[X(I—CC—Ph)4] mit X = Cl, Br, I, von PPh4[Br(Br—CC—Ph)4] und von NMe4[F(I—CC—Ph)2]
Authors: Ghassemzadeh Mitra , Harms Klaus , Dehnicke Kurt 
Published: July 2007

Complexes of Halide Ions with 1‐Halogen‐2‐phenylacetylenes. Crystal Structures of PPh4[X(I—CC—Ph)4] with X = Cl, Br, I, of PPh4[Br(Br—CC—Ph)4], and of NMe4[F(I—CC—Ph)2]Herrn Prof. Dr. H. Brunner zum 60. Geburtstag gewidmet.
The complexes PPh4[X(I—CC—Ph)4] with X = Cl (1), Br (2), I (3), PPh4[Br(Br—CC—Ph)4] (4), and NMe4[F(I—CC—Ph)2] (5) were prepared from the corresponding salts PPh4X and NMe4F, respectively, with the 1‐halogen‐2‐phenylacetylenes X—CC—Ph (X = Br, I) in dichloromethane solutions. 1—5 form colourless crystals, which were characterized by vibrational spectroscopy. According to the crystal structure determinations the halide ions in 1—4 are coordinated by the halogen atoms of the 1‐halogen‐2‐phenylacetylenes in a tetragonal‐pyramidal fashion. The fluoride ion in 5 is only twofold coordinated with a bond angle I—F—I of 110.45°.
Komplexe von Halogenid‐Ionen mit Diiodacetylen. Die Kristallstrukturen von PPh4[X(I‐CC‐I)2] mit X = Cl, Br, I
Authors: Ghassemzadeh Mitra , Harms Klaus , Dehnicke Kurt 
Published: July 2007

Complexes of Halide Ions with Diiodoacetylene. The Crystal Structures of PPh4[X(I‐CC‐I)2] with X = Cl, Br, IThe complexes PPh4[X(I‐CC‐I)2] with X = Cl (1), Br (2), and I (3) have been prepared from the phosphonium salts PPh4X and 1‐CC‐I in dichloromethane solutions. 1–3 form colourless crystals, which according to crystal structure analysis crystallize isotypically in the space group P421m with two formula units per unit cell. The diiodacetylenes are coordinated by the halide ions X− in a distorted tetragonal fashion, the I‐CC‐I molecules being in μ2‐bridging function. Thus, a polymeric anionic network [X(I‐CC‐I)2]nn− with a layered structure results.
Compounds of Germanium and Tin, 18. Cleavage Reactions of Hexa‐tert‐butylcyclotrigermane: Racemate versus Conglomerate Crystallization
Authors: Weidenbruch Manfred , Hagedorn Annette , Peters Karl , von Schnering Hans Georg 
Published: July 2007

AbstractTreatment of hexa‐tert‐butylcyclotrigermane (3) with CCl4, Br2, and I2 furnishes the correspondingly substituted 1,3‐dichloro‐ (4), 1,3‐dibromo‐ (5), and 1,3‐diiodotrigermanes (6). The symmetries of the molecules of 5 and 6 are very similar (point group C1) revealing gauche‐anti conformations and different GeGe bond lengths. However, while 5 crystallizes as a racemate, 6 forms a conglomerate of enantiomerically pure crystals. The X‐ray structure analysis of the 1,3‐dimethyltrigermane (7) derivative, derived from 6 by a sequence of metalation and methylation reactions, reveals more symmetrical molecules of the point group C2 which also crystallize as a racemate. Irradiation of 3 leads to tetra‐tert‐butyldigermene (8) and di‐tert‐butylgermylene (9) which could be trapped by addition and cycloaddition reactions with selenium, tellurium, and 3,5‐di‐tert‐butyl‐1,2‐benzoquinone.
The effect of substituting phosphorus for a ring carbon atom in the valence isomers cyclobutene, bicyclobutane, and 1,3‐butadiene. a quantum‐chemical investigation
Authors: Schoeller Wolfgang W. , Tubbesing Ulrike 
Published: July 2007

AbstractCyclobutene, bicyclobutane, and 1,3‐butadiene are valence isomers within the concept of the Woodward‐Hoffman rules. According to thermochemical considerations and in agreement with energy optimized quantum‐chemical calculations at the ab initio RHF and MP2/6‐31G(d,p) levels bicyclobutane is the least and 1,3‐butadiene the most stable valence isomer. Phosphorus substitution exerts a considerable effect on the relative stabilities of the various valence isomers. Bicyclobutanes containing phosphorus atoms in the bridgehead positions are considerably more stable than the other phosphorus‐substituted valence isomers. This conclusion was confirmed by an analysis of the natural bond populations.
Azolylborane adducts. Structural and conformational analysis by x‐ray diffraction and NMR. Protic‐hydric (CHδ+‐δ–HB) and Protic‐Fluoride (CHδ+‐δ–FB) interactions
Authors: Padilla‐Martińez Itzia Irene , Rosalez‐Hoz Maria De Jesús , Tlahuext Hugo , Camacho‐Camacho Carlos , Ariza‐Castolo Armando , Contreras Rosalinda 
Published: July 2007

AbstractThe preparation, NMR and X‐ray diffraction studies of a series of azolylboron hydrides derived from pyrrole, indole, and carbazole coordinated with tetrahydrofuran, pyridine, and imidazole are reported. The azolyl substituents are very electroattractive leading to an acidic boron atom which strongly coordinates with the Lewis bases. The stabilization of the BH2groups against disproportionation could be explained in terms of the interactions found between the acidic hydrogen atoms of the heterocycles (CHδ+ acceptor) and the hydrides (BHδ– donors).
Metal hydroborates and hydroborato metalates, 21. Solvates of lithium (dimethylamino)trihydroborate
Authors: Nöth Heinrich , Thomas Steffen , Schmidt Martin 
Published: July 2007

AbstractLi(Me2NBH3) (1) was prepared by deprotonation of Me2NH BH3 with LiBu and its solubility determined in various solvents. Compound 1 is unstable in most ethereal solvents and decomposes in a reversible reaction into LiH and Li‐(Me2NBH2NMe2BH3) (2). Five solvates of 1 were characterised by X‐ray structure analysis. Li(Me2NH3) · TMEDA is a dimer in the solid state, and two units are connected to one another by BH…Li bonds. The crystal structure of Li(Me2NBH3) · 0.5 dioxane is represented by layers consisting of tetrameric Li(Me2NBH3) units connected via dioxane molecules. Each Li atom is coordinated to one oxygen atom, one nitrogen atom, and two hydrogen atoms. Also Li(Me2NBH3) · 0.5 O2C3H6 forms an extended layer, however with pentacoordinated Li atoms which bear one oxygen, one nitrogen, and three hydrogen atoms. A similar layer structure was also found for Li(Me2NBH3) · O3C3H6 where each Li atom is bound to two oxygen atoms of different trioxane molecules, one nitrogen atom, and two hydrogen atoms. Finally, Li(Me2NBH3) · 12‐crown‐4 retains its molecular integrity in the solid state. Its Li atom is pentacoordinated by four oxygen atoms and one nitrogen atom.
Analysis of 13C and 17O Chemical Shift Tensors and an ELF View of Bonding in Fe2(CO)9 and Rh6(CO)16
Authors: Kaupp Martin 
Published: July 2007

AbstractCarbon and oxygen chemical shift tensors for bridging and terminal carbonyl ligands in Fe2(CO)9 and Rh6(CO)16 were calculated by sum‐over‐states density‐functional perturbation theory (SOS‐DFPT). Agreement with experimental 13C shift tensors is excellent, and 17O shift tensors are predicted. The reduced anisotropy values of the shift tensors for the bridging compared to terminal carbonyl ligands are due to large deshielding contributions to δ33 from non‐bonding or bridge‐bonding orbitals. Comparison to recent computational results for a series of unusual piano‐stool and bent‐sandwich group‐4 complexes is made. The electronic structures of the clusters are discussed by using plots of electron localization functions (ELF). Bonding electrons within the Rh6 cluster are mainly localized on the unbridged octahedral faces. This leads to a heterocubane‐like arrangement of ELF maxima above all octahedral faces (four bridging CO ligands, four M‐M 3‐center‐bonding maxima), in analogy to previous results for B6H62‐.
Synthesis and Reactivity of Bis(ethene) Rhodium(I) and Iridium(I) Carboxylato Complexes
Authors: Werner Helmut , Poelsma Sybo , Schneider Michael E. , Windmüller Bettina , Barth Dietmar 
Published: July 2007

Abstract[Rh(μ‐O2CCH3)(C2H4)2]2 (3) and analogous carboxylatobis‐(olefin)rhodium(I) complexes [Rh(μ‐O2CR)(olefin)2]2 (4–6) were almost quantitatively prepared under heterogeneous conditions from [RhCl(C8H14)2]2 (1) or [RhCl(C2H4)2]2 (2) and CH3CO2Na · 3 H2O or RCO2H/NaOH, respectively. The X‐ray crystal structure analysis of 3 confirmed the bridging position of the acetato ligands. The synthesis of [Ir(μ‐O2CCH3)(C2H4)2]2 (10) was carried out similarly by using [IrCl(C2H4)2]2 (8) and CH3CO2Na · 3 H2O as starting materials. The monoethene complex trans‐[Ir(η1‐O2CCH3)(C2H4)‐(PiPr3)2] (11) was obtained from 10 and PiPr3; it reacted with H2 and HCCPh by oxidative addition to give [IrH2(η2‐O2CCH3)(PiPr3)2] (12) and [IrH(CCPh)(η2‐O2CCH3)(PiPr3)2] (14), respectively. Compound 12 was also prepared from [IrH2Cl(PiPr3)2] (13) and CH3CO2Na · 3 H2O. The new bis‐(ethene)complexes 3, [Rh(μ‐O2CC6H5)(C2H4)2]2 (6) and 10 are catalytically less active than 2 in the reaction of C2H4 and Ph2CN2 and gave as C–C coupling product not only 1,1‐diphenylpropene (16) but also mixtures of 16 and 1,1‐diphenylcyclopropane (17) in different ratios.
Structure of O‐Methyl‐N,N‐bis(trifluoromethyl)hydroxylamine, (CF3)2NOCH3
Authors: Casper Bernd , Jakob Jens , Minkwitz Rolf , Oberhammer Heinz 
Published: July 2007

AbstractThe molecular structure of (CF3)2NOCH3 was determined by gas electron diffraction. The molecular intensities were reproduced by use of a single conformation with syn orientation of the O–CH3 group relative to the nitrogen lone pair. This was confirmed by ab initio calculations (HF/3‐21G(*), polarization functions only on nitrogen, and MP2/6‐31G*). The observed structure demonstrates that the generalized anomeric effect is of minor importance to this compound. The following skeletal geometric parameters (bond lengths [pm] and angles [°] with 3‐s̀ uncertainties) were derived: N–C 142.9(7), N–O 142(3), O–C 145(3), CNC 118.0(9), CNO 108.1(17), and NOC 109.4(17). The experimental structure is well reproduced by the ab initio calculations.