title: Density functional calculations on the conversion of azide and carbon monoxide to isocyanate and dinitrogen by a nickel to sulfur rebound mechanism.
abstract: Density functional calculations (B3 LYP & BP86) on a model system for the reaction between carbon monoxide and [Ni(N(3))('S(3)')](-) ('S(3)'(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, N(3) (-), and two sulfides are basal and the central S atom of the 'S(3)'(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 N(2) leaves as the remaining N atom and carbonyl rearrange to produce the nickel isocyanate product [Ni(NCO)('S(3)')](-).
authors.affiliation: Chemistry Department, Texas A&M University, College Station, TX 77843-3255, USA.
authors.forename: Yubo
authors.initials: Y
authors.lastname: Fan
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
mesh_terms: D001386:Azides / Q000138:chemical synthesis / Q000737:chemistry*; D002248:Carbon Monoxide / Q000737:chemistry*; D017953:Isocyanates / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry
chemical_list: D001386:Azides; D017953:Isocyanates; D009942:Organometallic Compounds; D013455:Sulfur; D009532:Nickel; D002248:Carbon Monoxide; D009584:Nitrogen