Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide.

An important challenge in the artificial fixation of N2 is to find atom efficient transformations that yield value-added products. Here we explore the coordination complex mediated conversion of ubiquitous species, CO and N2, into isocyanate. We have conceptually split the process into three steps: (1) the six-electron splitting of dinitrogen into terminal metal nitrido ligands, (2) the reduction of the complex by two electrons with CO to form an isocyanate linkage, and (3) the one electron reduction of the metal isocyanate complex to regenerate the starting metal complex and release the product. These steps are explored separately in an attempt to understand the limitations of each step and what is required of a coordination complex in order to facilitate a catalytic cycle. The possibility of this cyanate cycle was explored with both Mo and V complexes which have previously been shown to perform select steps in the sequence. Experimental results demonstrate the feasibility of some of the steps and DFT calculations suggest that, although the reduction of the terminal metal nitride complex by carbon monoxide should be thermodynamically favorable, there is a large kinetic barrier associated with the change in spin state which can be avoided in the case of the V complexes by an initial binding of the CO to the metal center followed by rearrangement. This mandates certain minimal design principles for the metal complex: the metal center should be sterically accessible for CO binding and the ligands should not readily succumb to CO insertion reactions.