Basische metalle: LII. Synthese von carbenoid- und ylidcobalt(III)-komplexen aus substitutionslabilen cobalt(I)-vorstufen |
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Authors: | L Hofmann H Werner |
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Institution: | Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-8700 Würzburg B.R.D. |
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Abstract: | The cyclopentadienylcobalt(I) compounds C5H5Co(PMe3)P(OR)3 (R = Me, Et, Pri) and C5H5Co(C2H4)L (L = PMe3, P(OMe)3, CO) are prepared by ligand substitution starting from C5H5Co(PMe3)2 and C5H5Co(C2H4)2. Whereas the reaction of C5H5Co(PMe3)P(OMe)3 with CH2Br2 mainly gives C5H5CoBr(PMe3)P(OMe)3]Br, the dihalogenocobalt(III) complexes C5H5CoX2(PMe3) (X = Br, I) are obtained from C5H5Co(CO)PMe3 and CH2X2. Treatment of C5H5Co(CO)PMe3 or C5H5Co(C2H4)PMe3 with CH2ClI at low temperatures produces a mixture of C5H5CoCH2Cl(PMe3)I and C5H5CoCl(PMe3)I, which can be separated due to their different solubilities. The same reaction in the presence of ligand L gives the carbenoidcobalt(III) compounds C5H5CoCH2Cl(PMe3)L]PF6 in nearly quantitative yields. If NEt3 is used as the Lewis base, the ylide complexes C5H5Co(CH2PMe3)(PMe3)X]PF6 (X = Br, I) are obtained. The PF6 salts of the dications C5H5Co(CH2PMe3)(PMe3)L]2+ (L = PMe3, P(OMe)3, CNMe) and C5H5Co(CH2PMe3)(P(OMe)3)2]2+ are prepared either from C5H5Co(CH2PMe3)(PMe3)X]+ and L, or more directly from C5H5Co(CO)PMe3, CH2X2 and PMe3 or P(OMe)3, respectively. The synthesis of C5H5CoCH2OMe(PMe3)I is also described. |
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