Catalytic Production of Isocyanates via Orthogonal Atom and Group Transfers Employing a Shared Formal Group 6 M(II)/M(IV) Redox Cycle

Under an atmosphere of CO, the Mo­(IV) imido complex Cp*Mo­[N­(iPr)­C­(Me)­N­(iPr)]­(NSiMe3) (Cp* = η5-C5Me5) (1) serves as a catalyst for production of an isocyanate via metal-mediated nitrene group transfer in benzene solution under mild conditions (55 °C, 10 psi) according to RN3 + CO → N2 + RNCO. Mechanistic and structural studies support a catalytic cycle for nitrene group transfer involving formal Mo­(II) monocarbonyl and Mo­(IV) (κ2-C,N)-isocyanate intermediates. These results complement an earlier finding that catalytic production of isocyanates can alternatively proceed through oxygen-atom transfer and an isomeric Mo­(IV) (κ2-C,O)-isocyanate according to N2O + CNR → N2 + RNCO.