title: Ir-catalysed asymmetric allylic substitutions with cyclometalated (phosphoramidite)Ir complexes--resting states, catalytically active (pi-allyl)Ir complexes and computational exploration.
abstract: Mechanistic aspects of allylic substitutions with iridium catalysts derived from phosphoramidites by cyclometalation were investigated. The determination of resting states by (31)P NMR spectroscopy led to the conclusion that the cyclometalation process is reversible. A novel, one-pot procedure for the preparation of (pi- allyl)Ir complexes was developed, and these complexes were characterised by X-ray crystal structure analyses and spectral data. They are fully active catalysts of the allylic substitution reaction. DFT calculations on the allyl complexes, transition states of the allylic substitution and product olefin complexes gave further mechanistic insight.
authors.affiliation: Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
authors.forename: Jevgenij A
authors.initials: JA
authors.lastname: Raskatov
authors.forename: Stephanie
authors.initials: S
authors.lastname: Spiess
authors.forename: Christian
authors.initials: C
authors.lastname: Gnamm
authors.forename: Kerstin
authors.initials: K
authors.lastname: Brödner
authors.forename: Frank
authors.initials: F
authors.lastname: Rominger
authors.forename: Günter
authors.initials: G
authors.lastname: Helmchen