- Chimie organometallique du niobium. Etude de la reactivite des complexes vinyliques 1=CHR2)>; acces a des complexes carbeniques 1,3-dithiol-2-ylidene niobium, precurseurs organiques
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The ?-alkenyl carbonyl complexes 1 1=CHR2> react with carbon disulfide giving the corresponding η2-CS2 complexes 2 2-CS2)CR1=CHR2)> 1 = R2 = CF3; 2b, R1 = R2 = CN; 2c, R1 = CF3, R2 = H; 2d, R1 = CN, R2 = H).Various 1,3-dithiol-2-ylidene complexes 3 1=CHR2)Nb= have been obtained from reactions of complexes 2 with a variety of activated alkynes R3CCR4 (R3 = R4 = CF3, CN, CO2Me, CO2Et; R3 = CN, CO2Me, R4 = H).The crystal and molecular structure of 3a 1 =R2 = R3 = R4 = CF3> has been determined by single-crystal X-ray diffraction.Crystal data are space group P212121, a 18.783(5), b 13.634(4), c 8.256(4) Angstroem, Z = 4.The dithioalkylidene ligand lies in a plane orthogonal to the plane of the alkenyl group; the later approximately bisects the Cp2Nb moiety.Decomplexation was achieved by reaction of complexes 3 1=CHR2)Nb= with iodine.In all cases with R2 = H, the resulting organic product 4 not only contains the carbene unit but also the vinyl group of 3.Analytical and spectroscopic data clearly supported the following formula for 4: When R1 = R2 = R3 = R4 = CF3, the decomplexation reaction with iodine only affords the tetrathiofulvalene: Other aspects of the chemistry of complexes 1=CHR2)(CO)> (1) are also briefly described. 1 react with cyclooctasulfur, dioxygen, phosphine and phosphite to give, via substitution of the carbonyl group by a two-electron ligand, complexes of general formula 1=CHR2)(Y)> with Y = s22-, O2-, PR3 or P(OR)3.
- Amaudrut, Jacques,Sala-Pala, Jean,Guerchais, Jacques, E.,Mercier, Rene
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- Fluorine segregation in crystalline materials: Structural control and solid-state [2+2] cycloaddition in CF3-substituted tetrathiafulvalene derivatives
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The well-known influence of long perfluorinated chains on the structures and stability of amphiphilic molecules in liquid crystalline mesophases or mesoscopic micellar arrangements is evaluated here in the realm of crystalline materials based on rigid aro
- Jeannin, Olivier,Fourmigue, Marc
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p. 2994 - 3005
(2008/09/16)
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- Halogen-Carbon-Sulfur Compounds: Synthesis and Modes of Reactions of 4,5-Bis(trifluoromethyl)-1,3-dithiole Derivatives
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The chemistry of the bis(trifluoromethyl)-1,3-dithiole system is thoroughly investigated starting from the 2-thione 6.By its oxidation the sulfine 2 and the ketone 7 are obtained.Further oxidation of 2 leads to the spiro compound 3.By chlorination of 6 th
- Maletzko, Christian,Sundermeyer, Wolfgang,Pritzkow, Hans,Irngartinger, Hermann,Huber-Patz, Ursula
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p. 2025 - 2031
(2007/10/02)
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- An Unusual Synthesis of Tetrakis(trifluoromethyl)tetrathiafulvalene
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Tetrakis(trifluoromethyl)tetrathiafulvalene (5) was formed in a phase-tranfer-catalyzed unusual one-step reaction by basic cleavage and subsequent alkylation of 1,3,4,6-tetrathiapentalene-2,5-dione (thiapendione) (1) with 2,3-dichlorohexafluoro-2-butene.As an example of the normal course of this reaction the synthesis of 4,5-(ethylenedithio)-1,3-dithiol-2-one (3) is described.
- Mueller, Harald,Lerf, Anton,Fritz, Heinz P.
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p. 395 - 396
(2007/10/02)
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- New Metal-assisted Synthesis of Tetrakis(trifluoromethyl)tetrathiafulvalene
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Replacement of the 1,3-dithiolium carbene ligand by CO or F3CCCCF3 in the complex > affords the complexes or , whereas the 1,3-dithioli
- Bianchini, Claudio,Meli, Andrea
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p. 1309 - 1310
(2007/10/02)
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