Cationic organozinc complexes of a bis(phosphinimine) pincer ligand: synthesis, structural and polymerization studies

Cationic organozinc complexes of a neutral bis(phosphinimine) pincer ligand (L) have been prepared and structurally characterized. This recently introduced ligand was constructed from a dibenzofuran (dbf) framework with symmetric attachment of phosphinimine groups at the 4 and 6 positions. Starting from protonated derivatives [LH][B(C(6)F(5))(4)] (1a), [LH][BPh(4)] (1b), or [LH(2)][BPh(4)](2) (1c), the complexes [LZnCH(3)][B(C(6)F(5))(4)] (2a), [LZnCH(3)][BPh(4)] (2b), and [LZnOAc][BPh(4)] (3), were prepared via protonolysis of an appropriate alkylzinc precursor. The complex [LZnPh][BPh(4)] (4) is generated as a side-product in the synthesis of 2b. Solid-state structural studies have revealed the compounds to be charge separated cationic zinc species with 3-coordinate trigonal planar geometry. Preliminary studies have shown these complexes to be inactive for the polymerization of lactide. Upon modification of the initiating group to a methyl-(S)-lactate, however, complex [LZnOCH(Me)CO(2)Me][B(C(6)F(5))(4)] (5) demonstrated significant polymerization activity at 60 degrees C. Additionally, NMR and mass spectrometry data confirmed a coordination-insertion mechanism was operative for this catalyst.