Stabilization of diazene in Fe(II)-sulfur model complexes relevant for nitrogenase activity. I. A new approach to the evaluation of intramolecular hydrogen bond energies
M. Reiher et al., Stabilization of diazene in Fe(II)-sulfur model complexes relevant for nitrogenase activity. I. A new approach to the evaluation of intramolecular hydrogen bond energies, THEOR CH AC, 106(6), 2001, pp. 379-392
A key step in the biological nitrogen fixation problem is the transfer of p
rotons and electrons onto inert molecular nitrogen. A first intermediate wi
ll then be diazene (diimide), N2H2, which is thermodynamically unstable wit
h respect to dissociation into N-2 and H-2 in the gas phase. Thus, diazene
must be stabilized such that the reduction of a complex binding an activate
d nitrogen becomes energetically feasible. A considerable contribution to t
his stabilization has been attributed to hydrogen bonds of the type N-H . .
.S. We investigate the strength of these hydrogen bonds in two model compo
unds. Since the contribution of an intramolecular hydrogen bridge to the to
tal binding energy of a molecule is not a well-defined concept, it is neces
sary to define a suitable descriptor for this quantity. We present a new ap
proach of estimating hydrogen-bond energies from two-center shared-electron
numbers obtained from density functional calculations. Our approach is par
ticularly designed for highly complex systems such as transition-metal comp
lexes with large coordination spheres.