title: Double geminal C-H activation and reversible alpha-elimination in 2-aminopyridine iridium(III) complexes: the role of hydrides and solvent in flattening the free energy surface.
abstract: [H2Ir(OCMe2)2L2]BF4 (1) (L = PPh3), a preferred catalyst for tritiation of pharmaceuticals, reacts with model substrate 2-(dimethylamino)pyridine (py-NMe2; py = 2-pyridyl) to give chelate carbene [H2Ir(py-N(Me)CH=)L2]BF4 (2a) via cyclometalation, H2 loss, and reversible alpha-elimination. Agostic intermediate [H2Ir(py-N(Me)CH2-H)L2]BF4) (4a), seen by NMR, is predicted (DFT(B3PW91) computations) to give C-H oxidative addition to form the alkyl intermediate [(H)(eta2-H2)Ir(py-N(Me)CH2-)L2]BF4. Loss of H2 leads to the fully characterized alkyl [HIr(OCMe2)(py-N(Me)CH2-)L2]BF4 (3a(Me2CO)), which loses acetone to give alkylidene hydride 2a by rapid reversible alpha-elimination. 2a rapidly reacts with excess H2 in d6-acetone to generate [H2Ir(OC(CD3)2)2L2]BF4 (1-d12), 3a((CD3)2CO), and py-NMe2 in a 1:1:1 ratio, showing reversibility and accounting for the selective isotope exchange catalyzed by 1. Reaction of 1 with py-N(CH2)4 gives the fully characterized carbene 2c. A cis-L(2) carbene intermediate, cis-2c, observed by NMR, reacts with CO via retro alpha-elimination to give the alkyl 3cCO, while the trans isomer, 2c, does not react; retro alpha-elimination thus requires the Ir-H bond to be orthogonal to the carbene plane. Consistent with experiment, computational studies show a particularly flat PE surface with activation of the agostic C-H bond giving a less stable H2 complex, then formation of a kinetic carbene complex with cis-L, only seen experimentally for py-N(CH2)4. Hydrides at key positions, together with gain or loss of solvent and H2, flatten the PE (DeltaG) surfaces to allow fast catalysis.
authors.affiliation: Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06520-810, USA.
authors.forename: Eric
authors.initials: E
authors.lastname: Clot
authors.forename: Junyi
authors.initials: J
authors.lastname: Chen
authors.forename: Dong-Heon
authors.initials: DH
authors.lastname: Lee
authors.forename: So Young
authors.initials: SY
authors.lastname: Sung
authors.forename: Leah N
authors.initials: LN
authors.lastname: Appelhans
authors.forename: Jack W
authors.initials: JW
authors.lastname: Faller
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree
authors.forename: Odile
authors.initials: O
authors.lastname: Eisenstein