A four coordinate parent imide via a titanium nitridyl
Chemical Communications, 2012•pubs.rsc.org
… Since our data provided inconclusive evidence for the parent imide … In this work, we
have demonstrated that incomplete reduction of the N 3 − ligand by ad 1 metal center still
results in N 2 extrusion with presumed formation of an electron deficient titanium nitridyl,
thereby providing entry to a rare example of a group 4 parent imide. Rather than undergoing
ligand radical ejection or N–N coupling to form an N 2 4 − ligand, H-atom abstraction (not
from solvent) appears to be the dominant pathway in formation the N–H bond. Current …
have demonstrated that incomplete reduction of the N 3 − ligand by ad 1 metal center still
results in N 2 extrusion with presumed formation of an electron deficient titanium nitridyl,
thereby providing entry to a rare example of a group 4 parent imide. Rather than undergoing
ligand radical ejection or N–N coupling to form an N 2 4 − ligand, H-atom abstraction (not
from solvent) appears to be the dominant pathway in formation the N–H bond. Current …
Treatment of d1 [(nacnac)TiCl(Ntol2)] with NaN3 results in NaCl formation and N2 ejection to yield the first four coordinate, parent imide [(nacnac)TiNH(Ntol2)] (nacnac−[ArNC(CH3)]2CH, Ar = 2,6-iPr2C6H3, tol = 4-CH3C6H4).
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