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- Title
Exceedingly Facile PhX Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms.
- Authors
Miloserdov, Fedor M.; McKay, David; Muñoz, Bianca K.; Samouei, Hamidreza; Macgregor, Stuart A.; Grushin, Vladimir V.
- Abstract
[(Ph3P)3Ru(L)(H)2] (where L=H2 ( 1) in the presence of styrene, Ph3P ( 3), and N2 ( 4)) cleave the PhX bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] ( 2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the PhI bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and PhI oxidative addition.
- Subjects
RUTHENIUM; CHEMICAL kinetics; AUTOCATALYSIS; CHEMICAL reactions; OXIDATIVE addition
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 29, p8586
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201501996