Alkyl and alkenyl arenes are used in a wide range of products. However, the synthesis of 1-phenylalkanes or their alkenyl variants from arenes and alkenes is not accessible with current commercial acid-based catalytic processes. Here, it is reported that an air-stable Rh(I) complex, (5-FP)Rh(TFA)(η²-C₂H₄) (5-FP = 1,2-bis(N-7-azaindolyl)benzene; TFA = trifluoroacetate), serves as a catalyst precursor for the oxidative conversion of arenes and alkenes to alkenyl
arenes that are precursors to 1-phenylalkanes upon hydrogenation. It has been demonstrated that coordination of the 5-FP ligand enhances catalyst longevity compared to unligated Rh(I) catalyst precursors, and the 5-FP-ligated catalyst permits in situ recycling of the Cu(II) oxidant using air. The 5-FP ligand provides a Rh catalyst that can maintain activity for arene alkenylation over at least 2 weeks in reactions at 150 °C that involve multiple Cu(II) regeneration steps using air. Conditions to achieve >13 000 catalytic turnovers with an 8:1 linear:branched (L:B) ratio have been demonstrated. In addition, the catalyst is active under aerobic conditions using air as the sole oxidant. At 80 °C, an 18:1 L:B ratio of alkenyl arenes has been observed, but the reaction rate is substantially reduced compared to 150 °C. Quantum mechanics (QM) calculations compare two predicted reaction pathways with the experimental data, showing that an oxidative addition/reductive elimination pathway is energetically favored over a pathway that involves C−H activation by concerted metalation−deprotonation. In addition, our QM computations are consistent with the observed selectivity (11:1) for linear alkenyl arene products.

Cyclic(alkyl)(amino) carbene (CAAC)-stabilized complexes of phosphorus, one of the lightest group 15 elements, are well-established and can often be obtained in high yields. In contrast, analogous CAAC compounds of bismuth, the heaviest nonradioactive member of group 15, are unknown. Indeed, reactivity increases as you descend the group, and as a result there are only a few examples of N-heterocyclic carbene (NHC)-bismuth complexes. Moreover, activated bismuth compounds often readily extrude bismuth metal, making isolation of stable complexes highly challenging. We report that CAACs react with phenylbismuth dichloride (PhBiCl₂) to afford ^Et2CAAC-Bi(Ph)Cl₂ and ^CyCAAC-Bi(Ph)Cl₂. Significantly, these complexes represent the first structurally characterized examples of CAAC-coordination to bismuth. The CAAC-stabilized bismuth compounds can also be obtained from air-stable salts, [^Et2CAAC-H]₂²⁺ [Cl₂(Ph)Bi(μ-Cl₂)Bi(Ph)Cl₂]²⁻ and [^CyCAAC-H]₂²⁺ [Cl₂(Ph)Bi(μ-Cl₂)Bi(Ph)Cl₂]²⁻, by deprotonation with potassium bis(trimethylsilyl)amide, K[N(SiMe₃)₂]. The electronic effects of the ligand on the bismuth center were investigated by comparing the CAAC-Bi(Ph)Cl₂ complexes to the NHC analogues, SIPr-Bi(Ph)Cl₂(THF) and IPr-Bi(Ph)Cl₂ (SIPr = 1,3- bis(2,6-diisopropylphenyl)-4,5-dihydroimidazole-2-ylidene; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene). Interestingly, the “normal” IPr-Bi(Ph)Cl₂ slowly isomerizes to the “abnormal” carbene complex, Cl2(Ph)Bi-IPr-H, at −37 °C. In the solid-state, the CAAC-, NHC-, and abnormal NHC-bismuth compounds exhibit Bi atomic centers in unique coordination environments. The complexes were fully characterized by NMR, elemental analysis, and single crystal X-ray diffraction studies. In addition, the bonding was probed by natural bond orbital (NBO) calculations.