Imido complexes formation from amines

Many routes to 0x0 and imido compounds have been developed. Transition metal-oxo complexes are coimnonplace and, in many cases, are the most stable form of an element in air. Some imido compoimds, including the first imido complex, have been prepared from metal-oxo complexes (Equation 13.50). The reactions of some of the later metal-oxo compounds with a primary amine generate an imido species by extrusion of water. In other cases, metal-imido complexes are prepared from 0x0 complexes by the reaction of phosphmimines (Equation 13.51) or from 0x0 or halo complexes by the reactions of silylamines (Equations 13.52 and 13.53). The driving force for these reactions is the formation of phosphine oxide, silyl ethers, or silyl halides. 

For M = Ru, formamides and amines were the principal products. Substitution of Fe3(CO)i2 for Ru3(CO)i2 results in the formation of carbamate esters (ArNHCOOMe) as the major products, with ureas as the main by-products. Without the metal carbonyl, nitroarenes are recovered imchanged from the reaction mixture. An imido-alcoxycarbonyl complex was suggested as an intermediate in the reaction and the difference between iron and ruthenium was proposed to be due to the different facility of this intermediate to undergo protonation and reductive elimination to give carbamate, or insertion of CO into the M-N bond, followed by hydrogenation, affording formamide (Scheme 13) ... 

---