title: Investigating CN- cleavage by three-coordinate M[N(R)Ar]3 complexes.
abstract: Three-coordinate Mo[N((t)Bu)Ar]3 binds cyanide to form the intermediate [Ar((t)Bu)N]3Mo-CN-Mo[N((t)Bu)Ar]3 but, unlike its N2 analogue which spontaneously cleaves dinitrogen, the C-N bond remains intact. DFT calculations on the model [NH2]3Mo/CN- system show that while the overall reaction is significantly exothermic, the final cleavage step is endothermic by at least 90 kJ mol(-1), accounting for why C-N bond cleavage is not observed experimentally. The situation is improved for the [H2N]3W/CN- system where the intermediate and products are closer in energy but not enough for CN- cleavage to be facile at room temperature. Additional calculations were undertaken on the mixed-metal [H2N]3Re+/CN- /W[NH2]3 and [H2N]3Re+/CN-/Ta[NH2]3 systems in which the metals ions were chosen to maximise the stability of the products on the basis of an earlier bond energy study. Although the reaction energetics for the [H2N]3Re+/CN /W[NH2]3 system are more favourable than those for the [H2N]3W/CN- system, the final C-N cleavage step is still endothermic by 32 kJ mol(-1) when symmetry constraints are relaxed. The resistance of these systems to C-N cleavage was examined by a bond decomposition analysis of [H2N]M-L1[triple bond]L2-M[NH2]3 intermediates for L1[triple bond]L2 = N2, CO and CN which showed that backbonding from the metal into the L1[triple bond]L2 pi* orbitals is significantly less for CN than for N2 or CO due to the negative charge on CN- which results in a large energy gap between the metal d(pi), and the pi* orbitals of CN-. This, combined with the very strong M-CN- interaction which stabilises the CN intermediate, makes C-N bond cleavage in these systems unfavourable even though the C[triple bond]N triple bond is not as strong as the bond in N2 or CO.
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
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D003486:Cyanides / Q000737:chemistry*; D008024:Ligands; D008956:Models, Chemical; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D003486:Cyanides; D008024:Ligands; D009942:Organometallic Compounds; D002248:Carbon Monoxide; D008982:Molybdenum; D009584:Nitrogen; D014414:Tungsten