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  • NMR spectroscopy  (6)
  • Platinum  (3)
  • Ab initio calculations  (2)
Materialart
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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 93-99 
    ISSN: 1434-1948
    Schlagwort(e): 2-Methyl-1,2,3,4-tetrazole-5-thiolates ; 2-Phenyl-1,2,3,4-tetrazole-5-thiolates ; Palladium ; Platinum ; Copper ; Silver ; Gold ; Molecular structures ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The molecular structures of nine transition metal tetrazolethiolates have been determined by X-ray structure determinations. The ligand is invariably coordinated through its sulfur atom to the metal center [M = PdII, CuI, AgI, AuI, AuIII, and Hg]. The M-S-C bond angles vary considerably, but this cannot be correlated with variations in the C-S bond lengths. Intermolecular association occurs for Ph3PAu(SCN4Me) via Au-S contacts, leading to dimeric strands in the solid state. The copper compound (Ph3P)3Cu4(SCN4Me)4 (5), possesses a rather asymmetric structure: one Cu atom is tricoordinated by 3 sulfur atoms, the other three are tetracoordinated by P and N as well as by S atoms.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1434-1948
    Schlagwort(e): α-Metallated amino acids ; Palladium ; Platinum ; Oxidative addition ; α-Bromoglycinate ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxidative addition of methyl N-benzoyl-2-bromoglycinate to bis(dibenzylideneacetone)palladium, in the presence of 2,2′-bipyridyl, and to (Ph3P)2Pt(η2-C2H4) gives the α-metallated glycine esters 1a and 2a. Abstraction of bromide from 1a, 2a, using AgSbF6 or AgBF4, affords the cationic C,O-chelate complexes [(bpy)Pd-CH(CO2Me)NHC(Ph)O]+ (1b,c) and [(Ph3P)2Pt-CH(CO2Me)NHC(Ph)O]+ (2b), respectively, featuring coordination of the amide O atom. The complexes 1b and 2b have been characterized by X-ray diffraction.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 517-521 
    ISSN: 1434-1948
    Schlagwort(e): Bis(silyl)phosphanes ; Magnesium ; NMR spectroscopy ; Oligomers ; Phosphorus ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The metathesis reaction of (dme)LiPH2 and chlorodiisopropylsilane yields HP(SiHiPr2)2 (1) and P(SiHiPr2)3 (2). The metalation of 1 by n/sec-dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [(3)2]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] (4) shows a dimer-trimer equilibrium in the 31P{1H}-NMR spectrum at -40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing-point depression in benzene yields a value of 516 g·mol-1, which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to -30°C leads to the precipitation of single crystals of monoclinic {(Me3Si)2P-Mg[μ-P(SiMe3)2]2}2Mg [(4)3].
    Materialart: Digitale Medien
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  • 4
    ISSN: 1434-1948
    Schlagwort(e): Arsenic ; Barium ; Calcium ; Metalations ; NMR spectroscopy ; Phosphorus ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran-O)calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me3Si)2NCa[μ-P(H)SiiPr3]3Ca(thp)3 (1) containing a trigonal-bipyramidal Ca2P3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or -arsane with bis(tetrahydrofuran-O)barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3, compounds of the type (thf)3Ba[μ-E(H)SiiPr3]Ba(thf)2E(H)SiiPr3 with E = P, As. The equimolar reaction of (tri-tert-butylsilyl)phosphane with (thf)2Ba[N(SiMe3)2]2 in toluene yields heteroleptic dimeric (thf)2Ba[N(SiMe3)2][P(H)SitBu3] (4). Addition of a further equivalent of H2PSitBu3 leads to the formation of homoleptic (thf)nBa[P(H)SitBu3]2 (5). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H2PSitBu3, yielding dimeric (thf)Ba3(PSitBu3)2[P(H)SitBu3]2 (6). The inner core of 6 consists of the tetramer (BaPSitBu3)4 based on a Ba4P4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)SitBu3]2 molecules.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 927-939 
    ISSN: 1434-1948
    Schlagwort(e): Bis(tetramethylpiperidino)aluminum halide complexes ; Tricoordinated aluminum cations ; 27Al-NMR spectroscopy ; X-ray crystal structure analysis ; Ab initio calculations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Upon treatment with Lewis bases Do (Do = pyridine bases or THF), the Lewis acids tmp2AlX (X = Cl, Br, I) are converted exclusively to the monoadducts tmp2AlX · Do (2-4). The Al-X bonds of these addition compounds are considerably elongated, indicating a tendency towards the formation of ionic species [tmp2Al(Do)]X. Due to the steric requirements of the bulky tmp ligands, addition of an excess of the Lewis base does not force these compounds to form tetracoordinated aluminum cations [tmp2Al(Do)2]+ or pentacoordinated adducts tmp2AlX · Do2. Attempts to prepare ionic representatives by reaction of tmp2AlX · Do with “ate” complexes of comparatively low nucleophilicity [MY = NaBPh4, AgBPh4, LiB(C6F5)4, AgBF4, AgOtos] result in phenylation products [e.g. tmp2AlPh (5a) and BPh3 · py (5b)] or tetracoordinated addition compounds tmp2AlY · Do (Y = anion). However, addition of one equivalent of AlX3 (X = Br, I) initiates halide abstraction with formation of the ionic [tmp2Al(Do)]AlX4 species 6a-f, as indicated by 27Al-NMR data and conductivity measurements. Solid [tmp2Al(py)]AlI4 (6b) decomposes readily into tmpAII2 and tmpAlI2 · py (7c). Addition of non-polar aliphatic solvents to solutions of [tmp2Al(Do)]AlX4 (6) leads to slow decomposition into tmp2AlX and AlX3 · Do (7a-b, d). This also occurs in polar donor solvents, where compounds AlX3 · Do are favoured due to the formation of penta- or hexacoordinated species AlX3 · Do · Solvn (n = 1, 2). Semiempirical AM1 calculations reveal the gas-phase stability of the tricoordinated bis(tmp)aluminum cation in the salt [tmp2AlPy]AlCl4 as the only representative in a series of calculated aluminum cations [(R2N)2AlPy]AlCl4 (R2N = Me2N, Et2N, iPr2N, tmp). According to these calculations, the stability of a given cation increases when tetrachloroaluminate is replaced by tetraiodoaluminate. Ab initio calculations have been performed on two cations [(H2N)2Al(Do)]+ (Do = NH3, py) and indicate very short Al-N bond lengths owing to ionic bonding contributions.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1434-1948
    Schlagwort(e): Cyclopentadienes ; Magnesium ; Metalations ; NMR spectroscopy ; Sandwich complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of n/sec-dibutyl magnesium with 6-methyl-6-phenyl- and 6,6-dicyclopropylfulvene gives the β-hydride transfer products 1,1′-bis(1-phenylethyl)- and 1,1′-bis-(dicyclopropylmethyl)magnesocene, respectively. The latter crystallizes in the eclipsed conformation, whereas the first one shows an anti conformation in the solid state. Dimethyl-magnesium deprotonates 6-methyl-6-phenylfulvene with formation of 1,1′-bis(1-phenylethen-1-yl)magnesocene, which decomposes upon isolation. The deprotonation of 6,6-dicyclopropylfulvene with MgMe2 in thf solution yields [bis(tetrahydrofuran-O)][iro{cyclopropane-1,2′(1′-η5-cyclopentadienyl-1′,3′,3′-tricyclopropyl-1′,2′,3′,3a′-tetrahydropentalene)}-3a′-6′-η2-enyl]magnesium. In the absence of β-hydrogen atoms at the organometallic reagent as well as at the fulvene the addition reaction is the only possible reaction pathway. Thus, one Mg-C bond of MgMe2 adds to tetramethylfulvene to give quantitatively dimeric methylmagnesium ethyltetramethylcyclopentadienide. The bridging methyl groups are sterically shielded against further attack of the fulvene.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1434-1948
    Schlagwort(e): Aminoalanes ; Alanes ; Ab initio calculations ; 27Al-NMR spectroscopy ; Structure elucidation ; Substituent effects ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions of metallated nucleophiles MIY [Y = OR, SR, NR2, PR2, AsR2, CR3, Si(SiMe3)3, R = organyl, H] with bis(2,2,6,6-tetramethylpiperidino)aluminum halides [tmp2AlX, (X = Cl, Br, I)] offer facile access to a variety of bis(amino)alanes of the type tmp2AlY. As indicated by 27Al-NMR spectroscopy, mass spectrometry and X-ray crystal structure determina-tions, all of these compounds are monomeric in the solid state, in solution, and in the gas phase. Even Al-E single bonds (E = Si, P, As etc.) that are not commonly encountered are stabilized by the supporting tmp fragments. The results of a systematic analysis of the bonding parameters determined for the tmp2AlY compounds, combined with a quantum mechanical study on model compounds (H2N)2AlY, not only reveal the presence of a highly polar Al-N bond, but at the same time rule out AlN-pp(π) bonding, in contrast to the situation in the analogous tmp2BY compounds. It is shown that the Al-N bond length depends on the acidic character of the protic species HY: the shorter d(Al-N), the less basic is Y.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1519-1527 
    ISSN: 1434-1948
    Schlagwort(e): B,B′-Dimesityldiborane(4) dihalides ; B,B′-Diamino-B,B′-dimesityldiboranes(4) ; B,B′-Di-tert-butyloxy-B,B′-dimesityldiborane(4) ; B,B′-Dimesityl-B,B′-di(organylthio)diborane(4) ; NMR spectroscopy ; X-ray structures ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An efficient route to B,B′-dihalo-B,B′-dimesityldiboranes(4) is reported, as well as the conversion of these and of B,B′-dimesityl-B,B′-dimethoxydiborane(4) into other B,B′-dimesityldiboranes B2mes2X2 (X = OR, SR, NR2, NHR). The substituents X influence the shielding of the 11B nucleus in the expected manner. Hindered rotation about the B-N bond is observed for X = pyrrolyl, while in solution there is free rotation about the B-C bond. However, X-ray structural results reveal that the mesityl group is almost orthogonal to the B(B)CY plane in the solid state. The shortest B-B bond is observed in mes2B2I2, indicating that the iodide is the strongest Lewis acid in the reported series of mes2B2Y2 compounds. This is also reflected in short B-C bonds. Moreover, the two mes(Y)B units also approach orthogonality in these diborane(4) compounds, and thus enforce this as a typical structural feature of diborane(4) derivatives. For this reason, the planar C(N)B-B(N)C unit of B,B′-di(benzylamino)-B,B′-dimesityldiborane(4) is regarded as exceptional for aminodiboranes(4).
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1791-1798 
    ISSN: 1434-1948
    Schlagwort(e): p-Ethynylphenylalanine ; Alkyne-bridged α-amino acids ; N,O-Chelate complexes ; Ferrocenes ; Schiff bases ; Platinum ; Gold ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The palladium-mediated coupling of p-ethynylphenylalanine (p-epa) with different halogenated benzenes yielded alkyne-bridged α-amino acids. A series of cationic mono- to hexanuclear (Ph3P)2Pt complexes with the anions of p-ethynylphenylalanine and alkynyl- or benzene-bridged di-, tri-, tetra- and hexa-ethynyl phenylalanines as N,O-chelate ligands was prepared. N-t-Boc-p-ethynylphenylalanine methyl ester was metal-substituted to give complexes of the types Ph3PAu-C≡C-R and (Et3P)2Pt(C≡CR)2. The benzene-bridged di-, tri-, tetra- and hexa-p-ethynylphenylalanine methyl esters form Schiff bases with ferrocene aldehyde and a tripodal ligand was obtained from Ph2PCH2CH2CH2NH2 and the benzene-bridged tri-ethynylphenylalanine. The structure of (Ph3P)2Pt[NH2C(H)(CH2C6H4C≡CH)CO2]+ BF4- was determined by X-ray diffraction.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1801-1805 
    ISSN: 0009-2940
    Schlagwort(e): Phosphene ; cyclophosphane isomerism ; Phosphorus Ylides ; NMR spectroscopy ; Structure elucidation ; Transanular interaction ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of two specific ylidyl dichlorophosphanes, Ph3P=CR-PCl2, with P(SiMe3)3 yields the ylidyl trimethylsilyl diphosphenes Ph3P=CR.P=P-SiMe3 as primary products which form two different types of dimers: the cyclotetraphosphane 9 (R = SiMe3), and the tetraphosphene 10 (R = 2,6-Cl, 2,/C6H3). The latter compound is readily converted to the bis(ylidyl)biocyclotetraphosphane 11. The molecular structures of 9 and 11 allow a strong transanular interaction between teh ylide-substituted phosphorus atoms, which results in very large two-bond coupling constants (2Jpp = 184 and 332 Hz respectively). The central P bond in 11 is relatively long (220.7 pm); quantum chemical calculations show the lengthening to be a consequence of the perpendicular orientation of the ylidic donor p-orbital.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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