Solution Structure and Dynamics of Hf–Al and Hf–Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain Transfer Reactions

Cationic cyclometalated hafnocenes [CpPrCpCH2CH2CH2Hf][B(C6F5)4] (4 Pr ) and [Cp iBuCpCH2CH(Me)CH2Hf][B(C6F5)4] (4a iBu and 4b iBu ) were synthesized from the corresponding [(CpPr)2HfMe][B(C6F5)4] (1 Pr ) and [(Cp iBu)2HfMe][B(C6F5)4] (1 iBu ) complexes via C-H activation. 4a iBu , 4b iBu , and 4 Pr , mimicking a propagating M-polymeryl species (M = transition metal) with or without a beta-methyl branch on the metalated chains, serve to investigate whether and how the nature of the last inserted olefin molecules changes the structure, stability, and reactivity of the corresponding heterobimetallic complexes, formed in the presence of aluminum- or zinc-alkyl chain transfer agents (CTAs), which are considered relevant intermediates in coordinative chain transfer polymerization (CCTP) and chain shuttling polymerization (CSP) technologies. NMR and DFT data indicate no major structural difference between the resulting heterobridged complexes, all characterized by the presence of multiple alpha-agostic interactions. On the contrary, thermodynamic and kinetic investigations, concerning the reversible formation and breaking of heterobimetallic adducts, demonstrate that isomer 4a iBu , in which the beta-Me is oriented away from the reactive coordination site on Hf, but not 4b iBu , having the beta-Me pointing in the opposite direction, is capable of reacting with CTAs. Quantification of kinetic rate constants highlights that the formation process is rate limiting and that the nature of the last inserted alpha-olefin unit modulates transalkylation kinetics. The reaction of 4a iBu , 4b iBu , and 4 Pr with diisobutylaluminum hydride (DiBAlH) allows the interception and characterization of new heterobinuclear and heterotrinuclear species, featuring both hydride and alkyl bridging moieties, which represent structural models of elusive intermediates in CCTP and CSP processes, capturing the instant when an alkyl chain has just transferred from a transition metal to a main group metal, while the two metals remain engaged in a single heterobimetallic intermediate.