RESUMO
Heteronuclear metal complexes comprising main group metals and transition metals have attracted widespread attention from researchers due to their applications in stoichiometric and catalytic activation of small molecules with possible cooperative effects. Herein, the advances of heterometallic complexes containing Mg- or Zn-metalloligands over the past ten years are reviewed. They consist of two parts: (i) synthetic approaches to heterometallic complexes. Only a brief discussion is made on the different Mg/Zn precursors since they have been summarized before. (ii) Stoichiometric and catalytic reactivities of heterometallic complexes containing Mg/Zn metalloligands. The exploration of the cooperative catalytic reaction of heterometallic complexes is still in its infancy, promising but challenging; thus, further investigations are required in the future.
RESUMO
This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)3 (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu2C6H3) and phosphines PR3 (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1/PEt3 pair at -30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH2SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.
