Journal
ORGANOMETALLICS
Volume 29, Issue 17, Pages 3817-3827Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om1004435
Keywords
-
Categories
Funding
- Israel Science Foundation
- European Research Council (ERC) [246837]
- Helen and Martin Kimmel Center for Molecular Design
Ask authors/readers for more resources
The complex (PNP)Ir-I(CH2COCH3) 2 (PNP = 2,6-bis((di-tert-butylphosphino)methyl)pyridine) was prepared by reaction of the dearomatized, electron-rich complex (PNP*)Ir-I(COE) (1; PNP* = deprotonated PNP, CUE = cyclooctene) with acetone. Upon treatment with CO, complex 2 undergoes a surprising elimination of acetone to form the dearomatized species (PNP*)Ir-I(CO) (4), involving proton migration from the ligand arm to the acetonyl moiety. DFT studies reveal that this process occurs via the square-pyramidal intermediate 2+CO, formed upon CO coordination to 2, in which the acetonyl moiety is located at the apical position prior to proton migration. Reaction of 2 with H-2 (D-2) indicates an equilibrium between complex 2 and the nonaromatic (PNP*)Ir-III(H)(CH2COCH3) complex 2b, which is the species that actually activates H-2 to exclusively form the trans-dihydride (PNP)Ir-III(H)(2)(CH2COCH3) (5a) and activates D-2 to form the trans-hydride-deuteride 5b with benzylic-D incorporation, as also corroborated by DFT studies. Interestingly, benzene C-H activation by complex 2 results in formation of the complex (PNP)Ir-I(C6H5) (6a) and elimination of acetone. DFT studies show that the benzene C-H bond is actually activated by the dearomatized bare (PNP*)Ir-I intermediate 2c, formed upon acetone elimination from 2.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available