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Synthesis and Reactivity of an Iridium(I) Acetonyl PNP Complex. Experimental and Computational Study of Metal−Ligand Cooperation in H−H and C−H Bond Activation via Reversible Ligand Dearomatization by Leonid Schwartsburd; Mark A. Iron; Leonid Konstantinovski; Yael Diskin-Posner; Gregory Leitus; Linda J. W. Shimon; David Milstein is a Chemistry article available to read on EtoBox.

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The complex (PNP)Ir I (CH 2 COCH 3 ) 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, COE = 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 squarepyramidal intermediate 2þCO, 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)(CH 2 COCH 3 ) complex 2b, which is the species that actually activates H 2 to exclusively form the trans-dihydride (PNP)Ir III (H) 2 (CH 2 COCH 3 ) (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 (C 6 H 5 ) (6a) and elimination of acetone. DFT stu

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Author

Leonid Schwartsburd; Mark A. Iron; Leonid Konstantinovski; Yael Diskin-Posner; Gregory Leitus; Linda J. W. Shimon; David Milstein

Publisher

American Chemical Society (ACS)

Published

2010

Language

EN

Field

Chemistry (Physical Sciences)