Mononuclear and Terminally Bound Titanium Nitrides

The
Ti­(III) azido complex (PN)2Ti­(N3) (PN– = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide),
can be reduced with KC8 to afford the nitride salt [μ2-K­(OEt2)]2[(PN)2TiN]2 in excellent yield. While treatment of the dimer with 18-crown-6
yields a mononuclear nitride, complete encapsulation of the alkali
metal with cryptand provides the terminally bound nitride as a discrete
salt [K­(2,2,2-Kryptofix)]­[(PN)2TiN]. All complexes
reported here have been structurally confirmed and also spectroscopically,
and the Ti–Nnitride bonding has been probed theoretically
via DFT-based methods.