Molecular titanium nitrides: nucleophiles unleashed.

In this contribution we present reactivity studies of a rare example of a titanium salt, in the form of [μ-K(OEt)][(PN)Ti[triple bond, length as m-dash]N] () (PN = -(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) to produce a series of imide moieties including rare examples such as methylimido, borylimido, phosphonylimido, and a parent imido. For the latter, using various weak acids allowed us to narrow the p range of the NH group in (PN)Ti[triple bond, length as m-dash]NH to be between 26-36. Complex could be produced by a reductively promoted elimination of N from the azide precursor (PN)TiN, whereas reductive splitting of N could not be achieved using the complex (PN)Ti[double bond, length as m-dash]N[double bond, length as m-dash]N[double bond, length as m-dash]Ti(PN) () and a strong reductant. Complete N-atom transfer reactions could also be observed when was treated with ClC(O)Bu and OCCPh to form NCBu and KNCCPh, respectively, along with the terminal oxo complex (PN)Ti[triple bond, length as m-dash]O, which was also characterized. A combination of solid state N NMR (MAS) and theoretical studies allowed us to understand the shielding effect of the counter cation in dimer , the monomer [K(18-crown-6)][(PN)Ti[triple bond, length as m-dash]N], and the discrete salt [K(2,2,2-Kryptofix)][(PN)Ti[triple bond, length as m-dash]N] as well as the origin of the highly downfield N NMR resonance when shifting from dimer to monomer to a terminal nitride (discrete salt). The upfield shift of N resonance in the N NMR spectrum was found to be linked to the K induced electronic structural change of the titanium-nitride functionality by using a combination of MO analysis and quantum chemical analysis of the corresponding shielding tensors.