Catalytic Production of Isocyanates via Orthogonal Atom and Group Transfers Employing a Shared Formal Group 6 M(II)/M(IV) Redox Cycle
dataset
posted on 2014-07-14, 00:00 authored by Brendan
L. Yonke, Jonathan P. Reeds, Philip P. Fontaine, Peter Y. Zavalij, Lawrence R. SitaUnder
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.
