Physics

Organic chemistry

Epoxide

Benzophenone

Stereochemistry

Radical

Catalysis

Lewis acids and bases

Chemistry

Electron paramagnetic resonance

Molecule

Nuclear magnetic resonance

Redox

Photochemistry

Journal of the American Chemical Society

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 Ldipp(Me)AlFp (2, Ldipp = HC{(CMe)(2,6-iPr2C6H3N)}2, Fp = FeCp(CO)2, Cp = η5-C5H5) was found to insert CO2 and cyclohexene oxide, producing LdippAl(Me)(μ:κ2-O2C)Fp (3) and LdippAl(Me)(μ-OC6H10)Fp (4), respectively. Detailed mechanistic studies indicate unusual pathways in which (i) the Al–Fe bond dissociates homolytically to generate formally AlII and FeI 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 Ldipp that stabilizes the formally AlII intermediates, instead giving them predominantly AlIII-like physical character. The redox noninnocent nature of the radical intermediates was elucidated through direct observation of LdippAl(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.

Cooperative Activation of CO<sub>2</sub> and Epoxide by a Heterobinuclear Al–Fe Complex via Radical Pair Mechanisms

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

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