Metallorganische Lewis-Säuren, LV [1] Darstellung und Reaktionen von Tetracarbonylmethyltetrafluoroboratoosmium, cis-(OC)4Os(FBF3)CH3/Organometallic Lewis Acids, LV [1] Preparation and Reactions of Tetracarbonylmethyltetrafluoroboratoosmium, cis-(OC)4Os(FBF3)CH3 (original) (raw)
Zeitschrift für Naturforschung B, 1991
Pentalithium Octa(ter/-butoxy)samarat(III), Synthesis, X-Ray [Li(tmed)]3[Sm (CH3)6] reacts with te/7-butanol in diethyl ether to give [Li5S m (0-r-C 4 H 9)8] (1), the structure o f which has been elucidated by X-ray structure analysis. 1 crystallizes tetragonally with a = 1703(4) and c-3178(1) pm, space group P 4,2,2, Z = 8. The structure was refined to R = 0.042 for 4082 observed reflections (F0 > 6 er(F0)).
Zeitschrift für anorganische und allgemeine Chemie, 2003
den als Reaktionsprodukt von 2 mit dem Silikon-Schliffett bei Kristallisationsversuchen von 2 erhalten. Beim Versuch, 2 mit CS 2 in THF umzusetzen wurde das THF-Spaltungsprodukt [HC(PPh 3) 2 ][CH 3 CH 2 CH 2 OCS 2 ] (7) in 60 %iger Ausbeute erhalten. Sämtliche Verbindungen wurden durch Einkristallstrukturanalysen charakterisiert, inklusive das bei der Darstellung von 3 angefallene Nebenprodukt [Br 3 Al{OP(C 6 H 5) 2 CH 2 P(C 6 H 5) 3 }][AlBr 4 ] (8) sowie die zur Synthese von 1 verwendete salzartige Verbindung [ClC(PPh 3) 2 ]Cl (9). tallize 2. Attempts to react 2 with CS 2 in THF gave the THFdecomposition product [HC(PPh 3) 2 ][CH 3 CH 2 CH 2 OCS 2 ] (7) in 60 % yield. All compounds were characterized by X-ray analyses including the byproduct [Br 3 Al{OP(C 6 H 5) 2 CH 2 P(C 6 H 5) 3 }][AlBr 4 ] (8) obtained during the preparation of 3 and the precursor compound for the synthesis of 1, the salt like compound [ClC(PPh 3) 2 ]Cl (9).
Zeitschrift für Naturforschung B, 1975
The organotin compounds Me3SnE(CF3)2, Me3SnE(H)CF3 and (Me3Sn)2ECF3 (Me = CH3, E = P, As) are obtained in good yield by the reaction of E2(CF3)4 and (CF3E)n (n = 4,5), respectively, with trimethylstannane.
Zeitschrift für Naturforschung B, 1996
The title compounds have been prepared from tetraphenylphosphonium chloride and N,N′- dimethylurea in acetonitrile using different molar ratios of the educts. Both compounds were characterized by IR spectroscopy and by crystal structure determinations. PPh4[Cl(H2,Me2,N2,CO)]: Space group P1̅, Z = 4 ,a = 1021.8(2), b = 1192.7(2), c = 2143.9(4) pm, α = 87.21(3)°, β = 85.95(3)°, γ = 74.16(3)° (-50°C). (PPh4)2[Cl(H2Me2N2CO)]Cl: Space group P21/n, Z = 4, a = 1138.4(2), b = 2855.4(3), c = 1394.0(1) pm, β = 91.19(10)° (-60°C). In both compounds the N.N′-dimethylurea molecule acts as a chelating Lewis acid via two Cl···H hydrogen bonds forming nearly planar ClH2N2C-six-membered heterocycles.
Zeitschrift für Naturforschung B, 1992
In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alky...
Zeitschrift für Naturforschung B, 1980
Mo(CO)5L complexes (L = R2EER2ʹ, R2EEʹR; R, Rʹ = CH3 and/or CF3; E = P, As; Eʹ = S, Se, Te) have been prepared by reaction of Mo(CO)5THF with L at room temperature. The new compounds were characterized by analytical and spectroscopic (IR, NMR, MS) methods.
Zeitschrift für Naturforschung B, 1991
In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)). Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identica...
Zeitschrift für Naturforschung B, 1992
The coordinating properties of dipod ligands of the type R2M′(OCH2PMe2)x(CH2CH2PMe2)2-x(R = Me, Ph; M' = Si, Ge; x = 0 -2) have been investigated by the preparation of the novel cis-M (CO)4L complexes (M = Cr, Mo, W). They are obtained under mild conditions in cyclohexane or n-hexane solution by the reaction of the norbornadiene precursors M(CO)4NBD with the corresponding ligands. In case of the Ge containing ligands the dilution principle was used to improve the yields of the mononuclear derivatives. The rate of the NBD replacement is mainly determined by the central atom M (Mo > W > Cr) and only little by R, M' or x . The new com pounds have been characterized by analytical (C, H) and spectroscopic investigations (1H, 31P NMR, IR, MS). The ligand properties are discussed on the basis of spectroscopic data (in particular coordination effects) and the molecular structure of the complexes Cr(CO)4[Ph2Si(OCH2PMe2)2] (12) and Mo(CO)4Me2Ge(CH2CH2PMe2)2] (28) obtained by X-r...
Zeitschrift für Naturforschung B, 1979
Element-element compounds of the general type RnE-ERm (R = CH3, CF3; E = P, As, S, Se, Te; n,m = 1, 2) have been prepared by different synthetic methods. New compounds were characterized by analytical and spectroscopic (NMR, MS) investigations. Information about the most suitable preparative route for all possible combinations is given in Tables I to III.
Stabile Methylenborane hoher Lewis-Acidität
Angewandte Chemie, 1989
belle 1, Reihe b bis d) und elektroneutralen Substraten (Reihe a) rnit ca. 3 kJ mol-' einheitlich kleiner als das bisher gefundene allgemeine Coulomb-Inkrement von 5 kJ mol-'.
Angewandte Chemie, 2014
Neue rein metallische Lewis-Paare (Metal-Only Lewis Pairs, MOLPs; Ru!Cr und Os!Cr) wurden durch Insertion nullwertiger Ruthenium-oder Osmiumkomplexe in die Chrom-Bor-Doppelbindung von Borylenkomplexen erhalten. Diese Reaktion führt zu neuen Borylenkomplexen (unter anderem zum ersten Osmiumborylenkomplex) und ist kristallisationskontrolliert: Das Auflçsen der Komplexe führt zur Rückbildung der Ausgangsverbindungen. Zusätzlich zu quantenchemischen Untersuchungen der ungewçhnlichen MOLPs wird auf Grundlage von DFT-Rechnungen auch ein Mechanismus für diese Rückreaktion vorgeschlagen.