C−H Bond Activation Reactions of Ethers That Generate Iridium Carbenes

Abstract

Two important objectives in organometallic chemistry are to understand C−H bond activation reactions mediated by transition metal compounds and then to develop efficient ways of functionalizing the resulting products. A particularly ambitious goal is the generation of metal carbenes from simple organic molecules; the synthetic chemist can then take advantage of the almost unlimited reactivity of this metal−organic functionality. This goal remains very difficult indeed with saturated hydrocarbons, but it is considerably more facile for molecules that possess a heteroatom (such as ethers), because coordination of the heteroatom to the metal renders the ensuing C−H activation an intramolecular reaction.

In this Account, we focus on the activation reaction of different types of unstrained ethers, both aliphatic and hemiaromatic, by (mostly) iridium compounds. We emphasize our recent results with the TpMe2Ir(C6H5)2(N2) (1·N2) complex (where TpMe2 denotes hydrotris(3,5-dimethylpyrazolyl)borate). Most of the reactivity observed with this system, and with related electronically unsaturated iridium species, starts with a C−H activation reaction, which is then followed by reversible α-hydrogen elimination. An α-C−H bond is, in every instance, broken first; when there is a choice, cleavage of the stronger terminal Csp3−H bonds is always preferred over the weaker internal Csp3−H (methylene) bonds of the ether. Nevertheless, competitive reactions of the unsaturated [TpMe2Ir(C6H5)2] iridium intermediate with ethers that contain Csp3−H and Csp2−H bonds are also discussed. We present theoretical evidence for a σ-complex-assisted metathesis mechanism (σ-CAM), although for other systems oxidative addition and reductive elimination events can be effective reaction pathways. We also show that additional unusual chemical transformations may occur, depending on the nature of the ether, and can result in C−O and C−C bond-breaking and bond-forming reactions, leading to the formation of more elaborate molecules.

Although the possibility of extending these results to saturated hydrocarbons appears to be limited for this iridium system, the findings described in this Account are of fundamental importance for various facets of C−H bond activation chemistry, and with suitable modifications of the ancillary ligands, they could be even broader in scope. We further discuss experimental and theoretical studies on unusual alkene-to-alkylidene equilibria for some of the products obtained in the reactions of iridium complex 1·N2 with alkyl aryl ethers. The rearrangement involves reversible α- and β-hydrogen eliminations, with a rate-determining metal inversion step (supported by theoretical calculations); the alkylidene is always favored thermodynamically over the alkene. This startling result contrasts with the energetically unfavorable isomerization of free ethene to ethylidene (by about 80 kcal mol−1), showing that the tautomerism equilibrium can be directed toward one product or the other by a judicious choice of the transition metal complex.