Cooperative Activation of CO₂ and Epoxide by a Heterobinuclear Al-Fe Complex via Radical Pair Mechanisms

Activation of inert molecules like CO₂ is often mediated by cooperative chemistry between two reactive sites within a catalytic assembly, the most common form of which is Lewis acid/base bifunctionality observed in both natural metalloenzymes and synthetic systems. Here, we disclose a heterobinuclear complex with an Al-Fe bond that instead activates CO₂ and other substrates through cooperative behavior of two radical intermediates. The complex L^dipp(Me)AlFp (2, L^dipp = HC{(CMe)(2,6-Pr₂C₆H₃N)}₂, Fp = FeCp(CO)₂, Cp = η⁵-C₅H₅) was found to insert CO₂ and cyclohexene oxide, producing L^dippAl(Me)(μ:κ₂-O₂C)Fp (3) and L^dippAl(Me)(μ-OC₆H₁₀)Fp (4), respectively. Detailed mechanistic studies indicate unusual pathways in which (i) the Al-Fe bond dissociates homolytically to generate formally Al^II and Fe^I metalloradicals, then (ii) the metalloradicals add to substrate in a pairwise fashion initiated by O-coordination to Al. The accessibility of this unusual mechanism is aided, in part, by the redox noninnocent nature of L^dipp that stabilizes the formally Al^II intermediates, instead giving them predominantly Al^III-like physical character. The redox noninnocent nature of the radical intermediates was elucidated through direct observation of L^dippAl(Me)(OCPh₂) (22), a metalloradical species generated by addition of benzophenone to 2. Complex 22 was characterized by X-band EPR, Q-band EPR, and ENDOR spectroscopies as well as computational modeling. The "radical pair" pathway represents an unprecedented mechanism for CO₂ activation.