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The first chiral amidinate borohydride rare earth compounds and compounds based on (S)-HPEBA ((S,S)-N,N-bis-(1-phenylethyl)benzamidine) ligand were reported by Roesky et al. To continuing this work, the new chiral ligand (S)-HNEBA ((S,S)-N,N-bis-(1-naphthylethyl)benzamidine) were synthesized. The corresponding amidinate metal complexes were successfully obtained by amine elimination. The luminescent and magnetic properties of rare earth compounds were studied. Alkaline earth metal compounds have been extensively studied as catalysts in synthetic chemistry. However, chiral amidinate alkaline earth metal complexes have never been reported. Chiral amidinate ligand (S)-HPEBA was introduced into the coordination chemistry of the alkaline earth metal as well as divalent lanthanides, their catalytic activities in hydrophosphination have been investigated. The Ba compound showed high catalytic activities in the hydrophosphination reaction. Moreover, since rare earth metal COT complexes exhibit excellent SMM behavior, it is of great interest to study the magnetic behavior of COT amidinate complexes. Thus, amidine ligand (S)-HPEBA and (S)-HPETA are introduced into the corresponding COT amidinate complexes for magnetic properties studies. The Er Compound exhibited typical field-induced SMM behavior. Furthermore, inspired by the promising application of lanthanide SMMs and the research of SMMs based on sandwich type lanthanide complexes, a series of novel sandwich type complexes comprising of Pc and COT ligand were designed and synthesized.
Bis(phosphinimino)methanide rare earth metal bisborohydrides, as illustrated in Scheme I, were successfully synthesized by salt metathesis reactions of [K{CH(PPh2NSiMe3)2}] with [Ln(BH4)3(THF)n] (Ln = Sc (n = 2); Ln = La, Nd, Lu (n = 3)) or in the case of yttrium by the reaction of [{(Me3SiNPPh2)2CH}YCl2]2 with NaBH4. Interestingly, the BH4- anions are ?3-coordinated in the solid state structures of 3, 4, 6 and 7, while for the scandium complex 5 two different conformational polymorphs were identified, in which either both BH4- groups are ?3-coordinated or one BH4- anion shows an ?2-coordination mode. Furthermore, complexes 3, 6 and 7 showed high activities in the ring-opening polymerization (ROP) of e-caprolactone (CL). At 0 °C, the molar mass distribution reached the narrowest values ever obtained for the ROP of CL initiated by a rare earth metal borohydride species.