Various new thermally air- and water-stable alkyl and aryl analogues of (acac-O,O)(2)Ir(R)(L), R-Ir-L (acac-O,O = kappa(2)-O,O-acetylacetonate, -Ir- is the trans-(acac-O,O)(2)Ir(III) motif, R = CH3, C2H5, Ph, PhCH2CH2, L = Py) have been synthesized using the dinuclear complex [Ir(mu-acac-O,O,C-3)-(acac-O,O)(acac-C-3)](2), [acac-C-Ir](2), or acac-C-Ir-H2O. The dinuclear Ir (III) complexes, [Ir(mu-acac-O,O,C-3)-(acac-O,O)(R)](2) (R = alkyl), show fluxional behavior with a five-coordinate, 16 electron complex by a dissociative pathway. The pyridine adducts, R-Ir-Py, undergo degenerate Py exchange via a dissociative mechanism with activation parameters for Ph-Ir-Py (Delta H double dagger = 22.8 +/- 0.5 kcal/mol; AS double dagger = 8.4 +/- 1.6 eu; Delta G double dagger(298K) = 20.3 +/- 1.0 kcal/mol) and CH3-Ir-Py (Delta H double dagger = 19.9 +/- 1.4 kcal/mol; Delta S double dagger = 4.4 +/- 5.5 eu; Delta G double dagger(298K) = 18.6 +/-0.5 kcal/mol). The trans complex, Ph-Ir-Py, undergoes quantitatively trans-cis isomerization to generate cis-Ph-Ir-Py on heating. All the R-Ir-Py complexes undergo quantitative, intermolecular CH activation reactions with benzene to generate Ph-Ir-Py and RH. The activation parameters (Delta S double dagger = 11.5 +/- 3.0 eu; Delta H double dagger = 41.1 +/- 1.1 kcal/mol; Delta G double dagger(298k) = 37.7 +/-1.0 kcal/mol) for CH activation were obtained using CH3-Ir-Py as starting material at a constant ratio of [Py]/[C6D6] = 0.045. Overall the CH activation reaction with R-Ir-Py has been shown to proceed via four key steps: (A) pre-equilibrium loss of pyridine that generates a trans-five-coordinate, square pyramidal intermediate; (B) unimolecular, isomerization of the trans-five-coordinate to generate a cis-five-coordinate intermediate, cis-R-Ir-square; (C) rate-determining coordination of this species to benzene to generate a discrete benzene complex, cis-R-Ir-PhH; and (D) rapid C-H cleavage. Kinetic isotope effects on the CH activation with mixtures of C6H6/C6D6 (KIE = 1) and with 1,3,5-C6H3D3 (KIE similar to 3.2 at 110 degrees C) are consistent with this reaction mechanism.