The discovery and development of organometallic catalysts is of paramount importance in modern organic synthesis, among which the ligand scaffolds play a crucial role in controlling the activity and selectivity. Over the past several decades, d8 transitionmetal complexes of pincer ligands have been developed extensively thanks to their easy structural modification, versatile reactivities, and high stability. One paradigm is the bis(phosphine)-based pincer iridium complexes PCP-Ir, which are highly active for alkane dehydrogenation, partly due to their high thermostability. However, except for alkane dehydrogenation and related transformations, few applications of pincer iridium catalysis have been seen in organic synthesis. This mainly arises from the low functional-group compatibility and poor substrate scope and the limited catalytic chemistry that invariably involves Ir(I/III) redox processes initiated by oxidative addition of substrates to 14-electron (PCP)Ir fragments (the proposed catalytically active intermediates). In this Account, we describe our endeavor on the development of a new family of PCN-Ir complexes with initial intention on creating more efficient alkane dehydrogenation catalysts. The replacement of a soft, Sigma donor phosphine arm in the PCP ligands by a harder, pi-acceptor N-heteroarene (pyridine or oxazoline) not only provides an additional platform to modify the structural properties but also offers new modes of bond activation and novel reactivities and catalysis. One uniqueness of the PCN-Ir system lies in the formation, via ortho-C(sp2)-H cyclometalation of the pyridine unit in the PCNPy ligand, of the neutral monohydride (PCC)IrIIIHL (L = neutral ligand), which catalyzes positional and stereoselective 1alkene-to-(E)-2-alkene isomerization. Moreover, the PCN-Ir catalysts effect ethanol dehydrogenation without decarbonylation, allowing for transfer hydrogenation of unactivated alkenes and trans-selective semihydrogenation of internal alkynes with userfriendly ethanol as the H-donor. Another feature originates from the ability of the pentacoordinate hydrido chloride complex (PCN)IrIIIHCl to undergo reversible solvent-coordination-induced-ionization (SCII), furnishing a cationic monohydride [(PCN)IrIIIH(Sol)]+Cl- bearing an uncoordinated Cl anion that effects selective hydrometalation of internal alkynes over the corresponding (Z)-alkenes; the resulting (PCN)IrIII(vinyl)Cl complex undergoes amine-assisted formal alcoholysis involving the protonation of the Cl anion by the activated IrIII-bound EtOH, again via the SCII pathway. Together these elementary reactions lay the foundation for cis-selective semihydrogenation of alkynes with EtOH. Further, the design of the oxazoline-containing chiral complexes (PCNOxa)IrIIIHCl enables asymmetric transfer hydrogenation of alkenes/ketones with ethanol. The efficient catalytic alpha alkylation of unactivated esters/amides with alcohols is another case showing the benefit that the PCN-Ir catalyst can offer. These examples illustrate the profound impact of the pincer ligands on the reactivities and catalysis. We hope this Account will provide an in-depth view into the fundamentals of pincer iridium chemistry and ultimately broaden its applications in organic synthesis.
