title: An experimental and theoretical investigation of the carbon dioxide insertion process into the tungsten-nitrogen bond of an anionic W(0) complex.
abstract: The pyridine bound 2-aminopyridine (2APH) derivative of tungsten pentacarbonyl has been prepared from photogenerated W(CO)5THF and 2APH. Deprotonation of the distal amine group by sodium hydride has provided two complexes, [Na][W(CO)5(2AP)] and [Na]2[W(CO)4(2AP)]2. Both complexes have been characterized by X-ray crystallography with the monomeric derivative being crystallized as its [Na2(18-crown-6)][W(CO)5(2AP)]2 salt which exhibits strong Na+...-NH interactions. Photolysis of W(CO)6 in the presence of excess 2-aminopyridine in THF has led to an efficient synthesis of the chelated neutral derivative, W(CO)4(2APH).2APH, where the extra equivalent of 2APH is hydrogen bonded to its bound counterpart. The 2-aminopyridine molecule of solvation was almost quantitatively removed via aqueous washings. Deprotonation of W(CO)4(2APH) with NaH afforded the amidopyridine derivative which was shown to rapidly undergo reaction with CO2 to yield the chelated carbamate complex, W(CO)4(OC(O)2AP)-. Nevertheless, because of the presence of small quantities of free 2-aminopyridine during the reactions with CO2, we have not been able to conclusively rule out participation by a ligand substitution process involving NC5H4NHCOOH. Ab initio computations were found to substantiate many of these experimental observations. That is, in the monodentate bound W(CO)5(2APH) derivative, binding through the pyridine nitrogen atom is favored by about 29 kJ/mol over the amine nitrogen atom, whereas the opposite site for binding is preferred for the deprotonated amido analogue, W(CO)5(2AP)-. Furthermore, both forms of W(CO)5(2AP)- were found to be more stable than the chelated tungsten tetracarbonyl anion plus CO. On the other hand, CO2 insertion into the W(CO)4(2AP)- anion to provide the chelated carbamate, W(CO)4(OC(O)2AP)-, was thermodynamically favored by >110 kJ/mol. Finally, both experimental and theoretical studies were inconclusive with regard to identifying reaction intermediates during the CO2 insertion pathway which involve prior interactions of CO2 at the amido nitrogen center.
authors: Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, USA.
authors: D J
authors: DJ
authors: Darensbourg
authors: B J
authors: BJ
authors: Frost
authors: D L
authors: DL
authors: Larkins