Lanthanide borohydrido complexes for MMA polymerization: syndio‐ vs iso‐ stereocontrol

In situ generated half-lanthanidocene based catalysts for the controlled oligomerisation of styrene: Selectivity, block copolymerisation and chain transfer

“…Another reason for the growing interest in borohydrido catalysts lies in their versatility and the related applicative potentialities for copolymerisations. They are indeed known as precatalysts for the polymerisation of dienes [24,25] and olefins [26] as well as initiators for polar monomers such as cyclic esters [27] and acrylates [28,29]. We reported recently the polymerisation of styrene by trisborohydrido complexes of the rare earths [30] and we present herein, in the course of our on-going research, preliminary results of the activity of an in-situ generated borohydrido half-neodymocene catalyst.…”

Syntheses of lanthanide monochloride and monoborohydride complexes supported by bridged bis(guanidinate) ligand and the use of borohydride complexes in polymerization of cyclic esters

“…Hydrogen atoms and the free THF molecules are omitted for clarity. 1 H NMR spectra of 6 and 7 are uninformative due to their paramagnetism of neodymium and ytterbium centers. Complexes 6e8 are sensitive to air and moisture, and are soluble in THF and toluene but sparingly soluble in n-hexane.…”

Bis(phosphinimino)methanide Borohydride Complexes of the Rare‐Earth Elements as Initiators for the Ring‐Opening Polymerization of ε‐Caprolactone: Combined Experimental and Computational Investigations

“…[22][23][24] Later on, greater value was given to these original species in the promotion of rare-earth borohydride organometallic chemistry [25][26][27][28] and in their use as efficient catalysts for the (co)polymerization of ethylene, [29][30][31] isoprene, [31][32][33][34][35] styrene, [34,36] and some polar monomers such as lactide, [37][38][39][40][41][42] e-caprolactone, [37][38][39][43][44][45][46][47][48][49][50][51][52] trimethylene carbonate, [52] and methyl methacrylate. [53][54][55][56][57] Also, some rare-earthmetal borohydride derivatives such as metallocenes, [31,46] mono-cyclopentadienyl complexes, [25,33,[35][36]…”