Abstract
The cyclometallation reaction known in the series of annulene heteroorganic ligands was extended to six-membered dihydroannulenes with a dinitrogen bridge. Double cyclopalladation of 4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-one azine yielded the first representative of a new class of cross-conjugated diazadipalladatetracycles,viz., 5,10-bis(acetylacetonato)-2,7-dimethyl-2,7-bis(trichloromethyl)-2,7-dihydro-4b,9b-diaza-5,10-dipalladaindeno[2,1-a]indene, isolated as a diastereomer mixture of the achiralmeso-form (E-isomer) and a racemate (Z-isomer). This reaction offers a method for transition metal-mediated activation of non-reactive C−H bonds at position 2 of cyclohexa-2,5-dienylidene systems and a route toward the very rare chiral polyheteroelement system with rotational symmetry.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1236–1239, June, 1997.
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Nikanorov, V.A., Kiktev, D.G., Storozhev, T.V. et al. Bis-para-semiquinoid type double cyclopalladation in the series of six-membered two-nitrogen bridged annulene-dihydroannulene ligands. Russ Chem Bull 46, 1187–1189 (1997). https://doi.org/10.1007/BF02496230
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DOI: https://doi.org/10.1007/BF02496230