Abstract

The Ti(III) azido complex (PN)(2)Ti(N-3) (PN- = (N-(2-(diisopropylphosphino)-4-Methylphenyl)-2,4,6-trimethylanilide), can be reduced with KC8 to, afford the nitride salt [mu(2)-K(OEt2)](2)[(PN)(2)Ti equivalent to 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)(2)Ti equivalent to N]. All complexes reported here have been,structurally confirmed and also spectroscopically, and the Ti-N-nitride bonding has been probed theoretically via DFT-based methods.