Cooperative bond activations by a tucked-in iron complex Joseph A. Zurakowski, Marcus W. Drover Department of Chemistry, Western University, London, Canada Diphosphines play a central role as supporting ligands in transition metal chemistry. To add to this burgeoning field, our team has placed an emphasis on preparing diphosphines having Lewis-acidic secondary coordination spheres (SCSs) for applications in sustainable transition metal reactivity. 1,2 During these studies, we have contrasted the reactivity of such Lewis-acid adorned diphosphine complexes with those devoid of Lewis- acidic functionality. We have made extensive use of the 1,2- bis (di-n-propylphosphino)ethane (dnppe) ligand framework, studying the reactivity of {M(R 2 PCH 2 CH 2 PR 2 )} where R = propyl or –CH 2 (CH 2 ) 2 BCy 2 (BCy 2 = Lewis- acid; Cy = cyclohexyl). With an eye towards uncovering unique reactivity with a boraneyl (–BR 2 ) decorated {Cp*Fe(diphosphine)} (Cp* = C 5 Me 5 – ) system, 3 we serendipitously discovered a highly reactive iron tucked- in complex, [(η 6 -C 5 Me 5 =CH 2 )Fe(dnppe)]. 4 This tucked-in complex displayed rich reactivity with a variety of electrophilic substrates including CO 2 , benzaldehyde, Br–Au I -PPh 3 , B(C 6 F 5 ) 3 , and HBCy 2 . Development of a CO 2 reduction cycle using this tucked-in complex is ongoing, in parallel with studies on other environmentally important small molecules such as ammonia (NH 3 ). This tucked-in system offers exciting prospects in the field of green chemistry, catalyzing the conversion of greenhouse gases and pollutants into value added products. Unveiling its rich reactivity could lead to a more sustainable future in chemical synthesis. 5 References 1. Drover, M.W. Chem. Soc. Rev. 2022 , 51 , 1861.
2. Zurakowski, J.A.; Austen, B.J.H.; Drover, M.W. Trends Chem. 2022 , 4 , 331. 3. Zurakowski, J.A.; Brown, K.R.; Drover, M.W.; Inorg. Chem. 2023 , 62 , 7053. 4. Zurakowski, J.A.; Drover, M.W. Chem. Commun. 2023 , in-press . DOI: 10.1039/D3CC03325B 5. Wheelhouse, K.M.P.; Webster, R.L.; Beutner, G.L. Organometallics 2023 , 42 , 1677.
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