Oxo/imido heterometathesis: From molecular stoichiometric studies to well-defined heterogeneous catalysts

[Display omitted] •Summary of stoichiometric oxo/imido heterometathesis reactions of imido complexes.•Current progress in the development of catalytic oxo/imido heterometathesis.•SOMC towards the design of well-defined silica-supported oxo and imido complexes. Oxo/imido heterometathesis is a class of reactions that interconvert terminal transition metal oxo and imido complexes via [2 + 2] cycloaddition/cycloreversion with heteroolefins and heterocumulenes containing oxo and imino groups. In this review we summarize the literature examples of stoichiometric oxo/imido heterometathesis reactions of imido complexes with different oxo substrates and discuss the current progress in the development of catalytic oxo/imido heterometathesis. In particular, we show how application of Surface Organometallic Chemistry approach allows preparation of highly efficient oxo/imido heterometathesis catalysts based on well-defined silica-supported early transition metal oxo and imido complexes.