Hydrogenation and silylation of a double-cyclometalated ruthenium complex

• Verfasst von: Scherl, Peter [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Hydrogenation and silylation of a double-cyclometalated ruthenium complex
• Titelzusatz: structures and dynamic behavior of hydrido and hydridosilicate ruthenium complexes
• Verf.angabe: Peter Scherl, Hubert Wadepohl, and Lutz H. Gade
• E-Jahr: 2013
• Jahr: July 22, 2013
• Umfang: 7 S.
• Fussnoten: Gesehen am 07.02.2022
• Titel Quelle: Enthalten in: Organometallics
• Ort Quelle: Washington, DC : ACS Publ., 1982
• Jahr Quelle: 2013
• Band/Heft Quelle: 32(2013), 15, Seite 4409-4415
• ISSN Quelle: 1520-6041
• DOI: doi:10.1021/om400574a
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1788650018

Abstract

A double-cyclometalated ruthenium complex containing a chiral tripodal phospholane has been prepared by reaction with [Ru(η4-COD)(η3-methylallyl)2] via elimination of isobutene. The ruthenium-carbon bonds of this compound were reversibly cleaved by H2, resulting in an equilibrium between a tri- and a tetrahydride (4 and 5). T1 relaxation time measurements revealed the nonclassical nature of the fluctuating hydrides. Release of the gas led to complete re-formation of the cyclometalated compound. Reaction of 3 with D2 afforded D10-5, in which six ortho-phenyl protons and four hydrides were replaced by deuterium. Furthermore, diphenylsilane was found to readily insert into one Ru-C bond to form 6, containing a κ3-dihydridosilicate fragment. On the basis of deuterium labeling experiments, the fast exchange between the two hydrides was shown to include a reductive elimination/oxidative addition step involving the remaining metalated phenyl group. Again, pressurization of 6 with H2 resulted in reversible cleavage of the remaining Ru-C bond, yielding the corresponding trihydride 7.