Rare‐Earth Metal Alkyl Complexes with 3‐Arylamido‐Functionalized Indolyl Ligands: Synthesis, Characterization and Reactivity†

Abstract

Summary of main observation and conclusionA series of dinuclear rare‐earth metal alkyl complexes {[μ‐η2:η1:η1‐3‐(LNCH)(CH2SiMe3)Ind]RE(CH2SiMe3)(THF)}2 (L1 = 2‐tBuC6H4, RE = Y, Gd, Dy, Er, Yb; L2 = 2,4,6‐Me3C6H2, RE = Dy, Er; Ind = indolyl) and {[μ‐η2:η1:η1‐3‐(LNCH2)Ind]RE(CH2SiMe3)(THF)}2 (L1, RE = Y, Dy, Er, Yb; L2, RE = Er, Yb) bearing 3‐arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE—C bond or by the alkane elimination reaction. In the preparation of above complexes, rare‐earth metal alkyl complexes [μ‐η5:η1:η1‐3‐(L2NCH)(CH2SiMe3)Ind]Gd(CH2SiMe3)(THF)}2 with a μ‐η5:η1:η1 coordination mode to the gadolinium ion and {[μ‐η3:η1:η1‐3‐(L2NCH2)Ind]Dy(CH2SiMe3)(THF)}2 with a μ‐η3:η1:η1 coordination mode to the dysprosium ion were unexpectedly isolated. The reactions of 3‐(L2N=CH)Ind with Er(CH2SiMe3)3(THF)2 at room temperature, generated a tetranuclear imino‐indolyl erbium intermediate {[μ‐η1:η1‐3‐(L2N=CH)Ind]Er(CH2SiMe3)2(THF)}4, which can transform into the amido functionalized indolyl erbium complex in hot toluene. Moreover, the reactivities of the newly synthesized ytterbium complex with N‐heterocyclic compounds were investigated, affording the corresponding products of the mixed pyridyl‐indolyl, imidazolyl‐indolyl, and ortho‐metalated complexes. The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1,4‐trans selectivity up to 91.7% and 1,4‐cis selectivity up to 96.1% in the presence of cocatalysts, respectively.