Reactivity of a functionalized trisamido ligand with Zr(NMe2)4 and GaMe3

NMR study of the reactivity of multifunctional ligand cis,cis-C6H9(NHCH2C6H4-o-PPh2)3 (1) with GaMe3 and Zr(NMe2)4 was carried out, yielding [cis,cis-(κN-NHCH2C6H4-o-PPh2)(κN-NCH2C6H4-o-PPh2)2C6H9]GaMe (2) and [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Ga2Me3 (3), and [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Zr(NMe2) (4), respectively. The spectral properties of 2 and 3 are very similar to that observed for the equivalent aluminum species already reported, but form at a much slower rate which allows for the observation of a GaMe3⋅1 adduct. Species 4 undergoes coordination/displacement of one of the phosphine arms, which was observed using both NMR spectroscopy and DFT analyses.

Graphical abstractLigand cis,cis-C6H9(NHCH2C6H4-o-PPh2)3 (1) was added to GaMe3 yielding [cis,cis-(kN-NHCH2C6H4-o-PPh2)(kN-NCH2C6H4-o-PPh2)2C6H9]GaMe (2) and [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Ga2Me3 (3) that have similar spectroscopic features than the equivalent aluminum species already reported, but forming at a slower rate. The reaction between (1) and Zr(NMe2)4 yields [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Zr(NMe2) (4) that undergoes coordination/displacement of one of the phosphine arms.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Coordination of C6H9(NHCH2C6H4-o-PPh2)3 to Ga occurs more slowly than the Al analogues. ► Coordination of C6H9(NHCH2C6H4-o-PPh2)3 to Zr yields a species with a phosphine Zr interaction. ► The Zr species undergoes coordination/displacement of one of the phosphine arms.