title: A comparison of N2 cleavage in Schrock's Mo[N3N] and Laplaza-Cummins' Mo[N(R)Ar]3 systems.
abstract: The four-coordinate Mo[N(3)N] complex, [N(3)N] = [{RNCH(2)CH(2)}(3)N], R = 3,5-(2,4,6-iPr(3)C(6)H(2))(2)C(6)H(3) (HIPT), which is capable of converting N(2) to ammonia catalytically, reacts with N(2) in a similar manner to Mo[N(R)Ar](3) (R = tBu, Ar = 3,5-C(6)H(3)Me(2)) to form a dinitrogen-bridged dimer intermediate, but unlike its three-coordinate counterpart, N(2) cleavage is not observed. To rationalise these differences, the reaction of N(2) with the model Mo[NH(2)](3)[NH(3)] and full ligand Mo[N(3)N] systems was explored using density functional theory and compared with the results of an earlier study involving the model three-coordinate Mo[NH(2)](3) system. Although the overall reaction is exothermic, the final N-N cleavage step is calculated to be endothermic by 75 kJ mol(-1) for the model system when the Mo-amine cap bond length is fixed to mimic the constraints of the ligand straps, but exothermic by 14 kJ mol(-1) for the full ligand system. In the latter case, the slightly exothermic cleavage step can be attributed to the destabilization of the N(2) bridged dimer relative to the nitride product owing to the steric effects of the bulky R groups. The activation barrier for N-N cleavage is estimated at 151 kJ mol(-1) for the model system, more than twice the calculated value for Mo[NH(2)](3), and even greater, 213 kJ mol(-1), for the full ligand [N(3)N]Mo system. A bonding analysis shows that although the binding of the amine cap helps to stabilize the intermediate dimer, at the same time it destabilizes the metal d-orbitals involved in backbonding to the pi* orbitals on N(2). As a result, backdonation is less efficient and N-N activation reduced compared to the three-coordinate system. Thus, the increased stability of the intermediate dimer on binding of the amine cap combined with the reduced level of N-N activation and higher kinetic barrier, explain why N-N cleavage has not been observed experimentally for the four-coordinate Mo[N(3)N] system.
authors.affiliation: Department of Chemistry, Faculty of Science, Australian National University, Canberra, ACT 0200, Australia.
authors.forename: Gemma
authors.initials: G
authors.lastname: Christian
authors.forename: Robert
authors.initials: R
authors.lastname: Stranger
authors.forename: Brian F
authors.initials: BF
authors.lastname: Yates