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Mechanistic Features of Iridium Pincer Complex Catalyzed Hydrocarbon Dehydrogenation Reactions:  Inhibition upon Formation of a μ-Dinitrogen Complex

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journal contribution
posted on 05.01.1998, 00:00 authored by Do W. Lee, William C. Kaska, Craig M. Jensen
Deuterium-labeling studies show that vinyl C−H oxidative addition of tert-butylethylene (tbe) to IrH2{C6H3-2,6-(CH2PBut2)2} (1) is rapid and reversible, while the stoichiometric hydrogenation of tbe by 1 is slower and irreversible. The dinitrogen complex, [Ir{C6H3-2,6-(CH2PBut2)2}]2(μ-N2) (3), results from the reaction of 1 with excess tbe under 1 atm of nitrogen. A single-crystal X-ray structure determination of 3 reveals a perpendicular arrangement of the P−C−P pincer ligands, which accounts for the surprising stability of 3 and the inhibiting effect of nitrogen on reactions catalyzed by 1.