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Cationic Ruthenium Hydrido−Carbonyls Derived from Metallocene-Based Pincers: Unusual Rearrangements and H2 Evolution with Formation of Cationic Ruthenium Metallocenylidenes

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posted on 2010-10-11, 00:00 authored by Avthandil A. Koridze, Alexander V. Polezhaev, Sergey V. Safronov, Alexey M. Sheloumov, Fedor M. Dolgushin, Mariam G. Ezernitskaya, Boris V. Lokshin, Pavel V. Petrovskii, Alexander S. Peregudov
Cationic ruthenium hydrido-carbonyls {RuH(CO)[tBuP,CH,PM]}BArF4 (M = Fe, 3; M = Ru, 4) (ArF = 3,5-(CF3)2C6H3) obtained in the reaction of H2 with RuCl(CO)[tBuP,C,PM] (M = Fe, 1; M = Ru, 2) in the presence of NaBArF4 add CO smoothly, giving the corresponding dicarbonyl complexes {RuH(CO)2[tBuP,CH,PM]}BArF4 (M = Fe, 11; M = Ru, 12). According to X-ray analysis of 11 and 12, addition of extra CO to complexes 3 and 4 leads to strengthening of the C(1)−H(1)···Ru(1) agostic interaction. Simultaneously, CO addition to 3 and 4 triggers a sequence (up to three steps) of unprecedented intramolecular rearrangements including migration of H atoms. First metallocenylidene complexes {Ru(CO)2[tBuP,C,PM]}BArF4 (M = Fe, 15; M = Ru, 16) were obtained in the course of these rearrangements accompanied by H2 evolution.

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