Nucleophilic Attack on Transition Metal Complexes of Carbon Monoxide and Isonitriles

These reactions are steps in the synthesis of organometallic complexes, in transformations for organic synthesis, and in the catalytic chemistry of CO. For example, the first synthesis of a carbene complex was achieved by a two-step sequence initiated by nucleophilic attack on a coordinated CO ligand. In addition, the production of CO and fi om 

CO and H O—the water-gas shift reaction—occurs by attack of water On a CO ligand that is coordinated to a heterogeneous iron catalyst in the commercial processes and to a soluble complex in many homogeneous systems.  

Effect of coordination, anciiiary iigands, and charge on the rate of nucieophiiic attack on CO. 

Examples of Nucleophilic Attack on Carbon Monoxide and Isonitriles 

A hydride is one of the simplest nucleophiles, and Casey ° and Gladysz have prepared kinetically stable formyl complexes by the direct attack of hydride on a number of neutral chromium-, molybdenum-, and iron-carbonyl complexes (Equation 11.2). Although these complexes are relatively electron rich, because they possess zero-valent metal centers, the negative charge in the product can be stabilized by the remaining -ir-ac-cepting CO ligands. 

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