Abstract
Properties and reactions of olefincobalt(0) complexes Co(C=C)L3 (L = PMe3; C=C = C2H4, C3H6, cyclopentene) are described. Reduction by potassium affords salts of the cobaltate anion Co(C=C)L3 - which upon protonation yield tbp complexes cis-CoH(C=C)L3. Formal insertion of olefin into the Co-H bond is demonstrated by H/D exchange and by catalytic isomerization of olefins. Complexes cis-CoCH3(C=C)L3 are thermally stable and do not give an analogous insertion reaction. In olefin cobaltates dinitrogen replaces the olefin to give dinitrogen cobaltates L3CoN2M (M = K, 1/2 Mg(THF)4). Electrophiles attack the ambidentate anion of these compounds,\({L_3}C\overline o = \mathop N\limits^ + = \overline N ,\), either at the cobaltate center (oxidative addition type) or at the terminal nitrogen (formation of diazenides L3Co-N=N-R, R = SiMe3, SnMe3).
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Klein, HF., Hammer, R., Wenninger, J., Gross, J. (1979). Trimethylphosphine Cobaltates Containing Monoolefin and Dinitrogen Ligands — Model Compounds for Homogeneous Catalysis. In: Pullman, B. (eds) Catalysis in Chemistry and Biochemistry Theory and Experiment. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, vol 12. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-9513-0_23
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DOI: https://doi.org/10.1007/978-94-009-9513-0_23
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