Experimental and Theoretical Insights into the Electronic Properties of Anionic N-Heterocyclic Dicarbenes through the Rational Synthesis of Their Transition Metal Complexes

The lithiation of the NHC ligand backbone in Cp(CO)2Mn(IMes) followed by transmetalation on C4 carbenic position with Cp(CO)2FeI led to heterobimetallic complex Cp(CO)2Mn(?-dIMes)Fe(CO)2Cp bearing anionic ditopic imidazol-2,4-diylidene dIMes ligand. Subsequent treatment later TfOH induced a selective decoordination [Cp(CO)2Mn] fragment form cationic abnormal [Cp(CO)2Fe(aIMes)](OTf), which was further derivatized bis(iron) [Cp(CO)2Fe(?-dIMes)Fe(CO)2Cp](OTf) reaction tAmOK and Cp(CO)2FeI. effect metalation at or C2 imidazole ring electronic donation properties associated centers quantified through systematic experimental theoretical studies IMes, aIMes, complexes. evaluation catalytic activity series Fe(II) complexes based ligands benchmark ketone hydrosilylation showed superiority bimetallic derivative.