The bonding of N-2 to the five-coordinate complexes [FeX(depe)(2)](+), X = Cl (1a) and Br (1b), has been investigated with the help of X-ray crystallography, spectroscopy, and quantum-chemical calculations. Complexes 1a and 1b are found to have an XP4 coordination that is intermediate between square-pyramidal and trigonal-bipyramidal. Mossbauer and optical absorption spectroscopy coupled with angular overlap model (AOM) calculations reveal that 1a and 1b have B-3(1) ground states deriving from a (xz)(1)(z(2))(1)configuration. The zero-field splitting for this state is found to be 30-35 cm(-1). In contrast, the analogous dinitrogen complexes [FeX(N-2)(dePe)(2)](+), X = Cl (2a) and Br (2b), characterized earlier are low-spin (S = 0; Wiesler, B. E.; Lehnert, N.; Tuczek, F.; Neuhausen, J.; Tremel, W. Angew. Chem, Int. Ed. 1998, 37, 815-817). N2 bonding and release in these systems are thus spin-forbidden. It is shown by density functional theory (DFT) calculations of the chloro complex that the crossing from the singlet state (ground state of 2a) to the triplet state (ground state of 1a) along the Fe-N coordinate occurs at r(C) = 2.4 Angstrom, Importantly, this intersystem crossing lowers the enthalpy calculated for N-2 release by 10-18 kcal/mol. The free reaction enthalpy DeltaGdegrees for this process is calculated to be 4.7 kcal/mol, which explains the thermal instability of N-2 complex 2a with respect to the loss of N-2. The differences in reactivity of analogous trans hydrido systems are discussed.