Recent studies of the LnA3/M reduction system (Ln = rare earth metal; A = anion; M = alkai metal) with Ln = Y and A = N(SiMe3)2 have provided EPR evidence for the existence of yttrium in the +2 oxidation state.  Using A = C5H4SiMe3 in the presence of a crown ether, it was possible to crystallographically characterize the first molecular Y2+ complex, [K(18-crown-6)][(C5H4SiMe3)3Y], via a LnA3/K reaction under argon.  Since Ho and Er are similar in size to Y, analogous syntheses were examined with these metals.  The synthesis of the first molecular Ho2+ and Er2+ complexes,  [K(18-crown-6)][(C5H4SiMe3)3Ho] and [K(18-crown-6)][(C5H4SiMe3)3Er], will be described as well as extension of this chemistry to the larger metal terbium, which would not be expected to form a divalent compound by K reduction since the calculated Tb3+/Tb2+ reduction potential is -3.7 V.  Factors affecting the stability of these divalent species will be discussed as well as their reactivity with dinitrogen.

Synthesis and structure of the first molecular complexes of Ho2+, Er2+, and Tb2+ and their reactivity with dinitrogen

243rd National Meeting (2012)

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