Title

"Effect of solvent and ancillary ligands on the catalytic H/D exchange reactivity of Cp*lr(L) complexes"

Document Type

Article

Publication Date

2013

Abstract

The reactivity of a series of Cp*IrIII(L) complexes that contain a diverse set of ancillary ligands, L, (L = PMe3, N-heterocyclic carbene, NHC = 1,3-dimethylimidazol-2-ylidene, aqua, 4-t-butylpyridine, and 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate) has been examined in catalytic H/D exchange reactions between C6H6 and a series of deuterated solvents (methanol-d4, acetic acid-d4, and trifluoroacetic acid-d1). These studies demonstrate that (1) the mechanism of catalytic H/D exchange is significantly influenced by the nature of the solvent; (2) electron-donating ligands (PMe3, NHC) promote the formation of Ir hydrides in methanol-d4, and these are critical intermediates in catalytic H/D exchange processes; and (3) weak/poorly donating ligands (4-t-butylpyridine, 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate and aqua) can support efficient H/D exchange catalysis in acetic acid-d4.

DOI

10.1021/cs400420n

Comments

Lehman, M. C.; Gary, J. B.; Boyle, P. D.; Sanford, M. S.; Ison, E. A. "Effect of solvent and ancillary ligands on the catalytic H/D exchange reactivity of Cp*lr(L) complexes" ACS Cata/. 2013, 3, 2304-2310.

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