TY - DATA T1 - Cationic Ruthenium Hydrido−Carbonyls Derived from Metallocene-Based Pincers: Unusual Rearrangements and H2 Evolution with Formation of Cationic Ruthenium Metallocenylidenes PY - 2010/10/11 AU - Avthandil A. Koridze AU - Alexander V. Polezhaev AU - Sergey V. Safronov AU - Alexey M. Sheloumov AU - Fedor M. Dolgushin AU - Mariam G. Ezernitskaya AU - Boris V. Lokshin AU - Pavel V. Petrovskii AU - Alexander S. Peregudov UR - https://acs.figshare.com/articles/journal_contribution/Cationic_Ruthenium_Hydrido_Carbonyls_Derived_from_Metallocene_Based_Pincers_Unusual_Rearrangements_and_H_sub_2_sub_Evolution_with_Formation_of_Cationic_Ruthenium_Metallocenylidenes/2723350 DO - 10.1021/om100667p.s001 L4 - https://ndownloader.figshare.com/files/4399318 KW - H 2 Evolution KW - Ru KW - H 2 evolution KW - First metallocenylidene complexes KW - intramolecular rearrangements KW - 4 triggers KW - RuH KW - NaBArF 4 KW - Cationic KW - complexes 3 KW - H 2 KW - Ruthenium KW - Fe KW - CF KW - H atoms KW - CO addition KW - dicarbonyl complexes KW - Unusual Rearrangements N2 - 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. ER -