Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO₂/Epoxide Copolymerization

The coordination chemistry of 4-(N,N-dimethylamino)pyridine (DMAP) with Salen- or Salan- (where the tetradentate N,N'-disubstituted bisaminophenoxide is designated as Salan, a saturated version of the Schiff-base Salen ligand) chromium complexes was studied by electrospray ionization mass spectrometry (ESI-MS). The relative stabilities of mono DMAP adducts of these chromium complexes were characterized by collision-induced dissociation (CID) and further discussed with regard to the activity in catalyzing CO(2)/epoxide copolymerization. [SalenCr](+) cations preferably bind two DMAP molecules to form six-coordinated complex ions, while [SalanCr](+) cations usually bind one molecule of DMAP to form five-coordinated complex ions, which were found to be relatively unstable. The remarkable difference in the coordination of DMAP to these two chromium complexes resulted in a significant difference in catalytic activity for the alternating copolymerization of CO(2) and propylene oxide. In the presence of 1 equiv of DMAP, the activity of the chromium-Salan complex 2a was up to 86 h(-1) of TOF at ambient temperature, which was about 30 times that of the corresponding chromium-Salen complex 1a. In sharp contrast to a long induction period up to 2 h with the use of 1a in conjunction with DMAP as catalyst, no initiation time or a very short one was observed in the binary 2a/DMAP catalyst systems. The initiator role of DMAP was confirmed by continuous determination of the propagating polymer species at various intervals using ESI-MS, which in combination with a kinetic study by means of infrared spectroscopy resulted in a mechanistic understanding on the difference in activity of the two catalyst systems for CO(2)/epoxide copolymerization.