Chiral Rh Diene NHC Complexes and Their Application in Rh-Catalyzed Cycloisomerization of Enynes

Surprisingly, both ligand classes are rarely employed together in Rh complexes. To get more detailed insight into the interaction between NHC and diene ligand simultaneously coordinated to the same Rh center, a series of eight neutral Rh diene NHC complexes, [Rh(L1)(NHC)Cl] (NHC = ICy, IMes, I^<i>i</i>Pr, IPr, SIPr, IMe, (<i>R</i>)-IEtPh, and (<i>S</i>)-IEtPh), and four cationic analogues, [Rh(L1)(NHC)]X (NHC = ICy, IMes, IPr: X = B(Ar^F)₄; NHC = ICy: X = SbF₆), were synthesized from [Rh(L1)Cl] by three complementary synthetic routes and anion exchange.

X-ray crystal structure analyses revealed pronounced NHC-dependent distortions from a square-planar geometry in neutral complexes, whereas cationic species remain comparatively rigid. Catalytic studies showed a strong dependence on the NHC ligand’s identity: while NHC incorporation generally reduced yields and enantioselectivities in asymmetric 1,2- and 1,4-additions, the cationic complex [Rh(L1)(ICy)]SbF₆ delivered improved activity and selectivity in 1,6-enyne cycloisomerization, consistent with reduced catalyst deactivation as confirmed by kinetic analysis.