Two-coordinate silylamido complexes of nickel and copper rapidly react with CO to selectively form a new cyanate ligand along with hexamethyldisiloxane byproducts. Mechanistic insight into these reactions was obtained from the synthesis of proposed intermediates, several silyl- and phenyl- substituted amido analogues, and their subsequent reactivity with CO. These studies suggest that a unique intramolecular double silyl transfer step facilitates CO deoxygenation, which likely contributes to the rapid rates of reaction. The deoxygenation reactions create a platform for a synthetic cycle in which copper amido complexes convert CO to organic silylcarbamates.
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