Dehydropolymerization of H3B·NMeH2Mediated by Cationic Iridium(III) Precatalysts Bearing κ3-iPr-PNRP Pincer Ligands (R = H, Me):An Unexpected Inner-Sphere Mechanism

The dehydropolymerization of H3B·NMeH2to form N-methylpolyaminoborane using neutral and cationic catalysts based on the {Ir(iPr-PNHP)} fragment [iPr-PNHP = κ3-(CH2CH2PiPr2)2NH] is reported. Neutral Ir(iPr-PNHP)H3or Ir(iPr-PNHP)H2Cl precatalysts show no, or poor and unselective, activity respectively at 298 K in 1,2-F2C6H4solution. In contrast, addition of [NMeH3][BArF4] (ArF= 3,5-(CF3)2C6H3) to Ir(iPr-PNHP)H3immediately starts catalysis, suggesting that a cationic catalytic manifold operates. Consistent with this, independently synthesized cationic precatalysts are active (tested between 0.5 and 2.0 mol % loading) producing poly(N-methylaminoborane) with Mn∼40,000 g/mol, D ∼1.5, i.e., dihydrogen/dihydride, [Ir(iPr-PNHP)(H)2(H2)][BArF4]; σ-amine-borane [Ir(iPr-PNHP)(H)2(H3B·NMe3)][BArF4]; and [Ir(iPr-PNHP)(H)2(NMeH2)][BArF4]. Density functional theory (DFT) calculations probe hydride exchange processes in two of these complexes and also show that the barrier to amine-borane dehydrogenation is lower (22.5 kcal/mol) for the cationic system compared with the neutral system (24.3 kcal/mol). The calculations show that the dehydrogenation proceeds via an inner-sphere process without metal-ligand cooperativity, and this is supported experimentally by N-Me substituted [Ir(iPr-PNMeP)(H)2(H3B·NMe3)][BArF4] being an active catalyst. Key to the lower barrier calculated for the cationic system is the outer-sphere coordination of an additional H3B·NMeH2with the N-H group of the ligand. Experimentally, kinetic studies indicate a complex reaction manifold that shows pronounced deceleratory temporal profiles. As supported by speciation and DFT studies, a key observation is that deprotonation of [Ir(iPr-NHP)(H)2(H2)][BArF4], formed upon amine-borane dehydrogenation, by the slow in situ formation of NMeH2(via B-N bond cleavage), results in the formation of essentially inactive Ir(iPr-PNHP)H3, with a coproduct of [NMeH3]+/[H2B(NMeH2)2]+. While reprotonation of Ir(iPr-PNHP)H3results in a return to the cationic cycle, it is proposed, supported by doping experiments, that reprotonation is attenuated by entrainment of the [NMeH3]+/[H2B(NMeH2)2]+/catalyst in insoluble polyaminoborane. The role of [NMeH3]+/[H2B(NMeH2)]+as chain control agents is also noted.