| Sumario: | Experiments and density functional calculations were used to quantify the impact of the Pd--Ti interaction in the cationic heterobimetallic ClTi(NBuPPh)Pd(η³-methallyl) catalyst 1 used for allylic aminations. The catalytic significance of the Pd--Ti interaction was evaluated computationally by examining the catalytic cycle for catalyst 1 with a conformation where the Pd--Ti interaction is intact versus one where the Pd--Ti interaction is severed. Studies were also _oo_ '-- performed on the relative reactivity of the cationic monometallic (CH)(NBuPPh)Pd(η³-methallyl) catalyst 2 where the Ti from catalyst 1 was replaced by an ethylene group. These computational and experimental studies revealed that the Pd--Ti interaction lowers the activation barrier for turnover-limiting amine reductive addition and accelerates catalysis up to 10. The Pd--Ti distance in 1 is the result of the N'Bu groups enforcing a boat conformation that brings the two metals into close proximity, especially in the transition state. The turnover frequency of classic Pd π allyl complexes was compared to that of 1 to determine the impact of P--Pd--P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh)Pd(η³-CHC(CH)CH) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal that the apparent similarity in reactivity is due to very fast reaction kinetics. The higher reactivity of 1 versus 3 was confirmed in the reaction of methallyl chloride and 2,2,6,6-tetramethylpiperidine (TMP). Overall, experiments and calculations demonstrate that the Pd--Ti interaction induces and is responsible for significantly lower barriers and faster catalysis for allylic aminations.
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