The application of a diamide-diimine ligand, dadin (i.e., {2-(2,6-iPr-C6H3)-C6H4}NCCN{C6H4-2-(2,6-iPr-C6H3)}) to first row early transition metals will be reported. (dadi)TiL (L = THF, PMe2Ph, Cl-) have been synthesized from TiCl2(TMEDA)2 and M2(dadi) (M = Li, Na), and (dadi)TiPMe2Ph and [(dadi)TiCl][Li(THF)4] were structurally characterized. THF adduct (dadi)Ti(THF) does not bind CO, and catalyzes the conversion of Ad-N3 (Ad = adamantyl) and CO to Ad-NCO + N2; (dadi)Ti=NAd was isolated in the absence of CO. Efforts to make an oxo derivative are ongoing, as are related reactions with (dadi)V derivatives.

Early metal chemistry featuring redox non-innocent (RNI) ligands

251st National Meeting (2016)

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