Density Functional Calculations on the Conversion of Azide and Carbon Monoxide to Isocyanate and Dinitrogen by a Nickel to Sulfur Rebound Mechanism

Authors:
Publisher website
Google Scholar
Abstract
Density functional calculations (B3 LYP & BP86) on a model system for the reaction between carbon monoxide and [Ni(N3)(′S3′)]− (′S3′2−=bis(2‐mercaptophenyl)sulfide (2−)) predict a three‐step mechanism. First, CO attacks the nickel to generate a pseudo “square‐pyramidal” complex, in which CO, N3−, and two sulfides are basal and the central S atom of the ′S3′2− ligand backs away from Ni to form a weak NiS apical bond. Then, CO inserts into the NiN bond and the weak apical NiS bond rebounds to its original strength as the nickel forms a square‐planar intermediate. Finally, in a one‐step process N2 leaves as the remaining N atom and carbonyl rearrange to produce the nickel isocyanate product [Ni(NCO)(′S3′)]−.

This publication has 55 references indexed in Scilit: