Solution Structure and Dynamics of Hf-Al and Hf-Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain...

Cationic cyclometalated hafnocenes [Cp^PrCp^CH2CH2CH2Hf][B(C₆F₅)₄] (4) and [CpCp^CH2CH(Me)CH2Hf][B(C₆F₅)₄] (4a and 4b) were synthesized from the corresponding [(Cp^Pr)₂HfMe][B(C₆F₅)₄] (1) and [(Cp)₂HfMe][B(C₆F₅)₄] (1) complexes via C-H activation. 4a, 4b, and 4, mimicking a propagating M-polymeryl species (M = transition metal) with or without a β-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 α-agostic interactions. On the contrary, thermodynamic and kinetic investigations, concerning the reversible formation and breaking of heterobimetallic adducts, demonstrate that isomer 4a, in which the β-Me is oriented away from the reactive coordination site on Hf, but not 4b, having the β-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 α-olefin unit modulates transalkylation kinetics. The reaction of 4a, 4b, and 4 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.