Influence of the metal (Al, Cr, and Co) and the substituents of the porphyrin in controlling the reactions involved in the copolymerization of propylene oxide and carbon dioxide by porphyrin metal(III) complexes. 2. Chromium chemistry.

The reactivities of chromium(III) complexes LCrX, where L = 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP), and 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) and X = Cl or OH, have been studied with respect to their ability to homopolymerize propylene oxide (PO) and copolymerize PO and CO(2) to yield polypropylene oxide (PPO) and polypropylene carbonate (PPC) or propylene carbonate (PC), respectively, with and without the presence of a cocatalyst, namely, 4-dimethylaminopyridine (DMAP) or PPN(+)Cl(-) (bis(triphenylphosphine)iminium chloride). The homopolymerization is notably faster (TOF ≈ 2000 h(-1) at room temperature) than copolymerization, which commonly leads to ether-rich polymers. Studies of kinetics reveal that for TPPCr(OH) with DMAP (1 equiv) the propagation reaction rate is first order in [Cr] with excess PO. With PPN(+)Cl(-) as a cocatalyst the reaction order in [Cr] and [Cl(-)] is complicated by the presence of two growing chains, and the presence of excess [Cl(-)] facilitates the formation of PC by two different backbiting mechanisms. The fixation of CO(2) is promoted by [Cl(-)] but is not greatly influenced by CO(2) pressure (1-50 bar). The reactions and polymers have been monitored by UV-visible spectroscopy, react-IR, GPC, ESI, and MALDI TOF, and NMR ((1)H, (13)C{(1)H}) spectroscopy. Notable differences are seen in these reactions when compared with earlier studies by Darensbourg et al. with salen chromium(III) systems and related aluminum(III) porphyrins.