Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐RhIII(CF2)4 (2) was prepared from PBP‐RhI‐PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−CF bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−CF bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−RhIII(CF2)4 (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−CF bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−CF bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.

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Developing novel polymers with biodegradability could mitigate polymer-related pollution. Here, polymers containing ester and ketone groups with moderate biodegradability (regardless of their chirality) were synthesized from poly(propylene-alt-carbon monoxide)s by the Baeyer–Villiger oxidation with aqueous H2O2 and AlCl3 (which increased the ester content of the as-synthesized polymers to >35 mol%). The ester groups in these polymers, showed two isomeric structures (originating from two oxygen-atom insertion modes), and 70% of the ester groups were structurally same as those in P3HB (a common biodegradable polymer). Additionally, solvent-cast blended films comprising these polymers and poly(L-lactic acid) showed a higher strain at break than pure-poly(L-lactic acid) films. Therefore, this study proposes a cost-effective strategy for the synthesis of biodegradable polymers that can be used as plasticizers of poly(L-lactic acid), facilitating a wide range of applications.

Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐RhIII(CF2)4 (2) was prepared from PBP‐RhI‐PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−CF bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−CF bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−RhIII(CF2)4 (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−CF bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−CF bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.