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

• Hall, Michael

published proceedings

• Chemistry

author list (cited authors)

• Fan, Y., & Hall, M. B.

citation count

• 13

complete list of authors

• Fan, Yubo||Hall, Michael B

publication date

• April 2004

publisher

• Wiley  Publisher

published in

• Chemistry - A European Journal  Journal

keywords

• Azides
• Carbon Monoxide
• Isocyanates
• Models, Chemical
• Molecular Conformation
• Nickel
• Nitrogen
• Organometallic Compounds
• Sulfur

PubMed Central ID

• 15054768

Digital Object Identifier (DOI)

• 10.1002/chem.200304840

start page

• 1805

end page

• 1814

volume

• 10

issue

• 7

URL

• https://doi.org/10.1002/chem.200304840