Expanding yttrium bis(trimethylsilylamide) chemistry through the reaction chemistry of (N2)2-, (N2)3-, and (NO)2- complexes.

ABSTRACT

The reaction chemistry of the side-on bound (N(2))(2-), (N(2))(3-), and (NO)(2-) complexes of the [(R(2)N)(2)Y](+) cation (R = SiMe(3)), namely, [(R(2)N)(2)(THF)Y](2)(µ-η(2)η(2)-N(2)), 1, [(R(2)N)(2)(THF)Y](2)(µ-η(2)η(2)-N(2))K, 2, and [(R(2)N)(2)(THF)Y](2)(µ-η(2)η(2)-NO), 3, with oxidizing agents has been explored to search for other (E(2))(n-), (E = N, O), species that can be stabilized by this cation. This has led to the first examples for the [(R(2)N)(2)Y](+) cation of two fundamental classes of [(monoanion)(2)Ln](+) rare earth systems (Ln = Sc, Y, lanthanides), namely, oxide complexes and the tetraphenylborate salt. In addition, an unusually high yield reaction with dioxygen was found to give a peroxide complex that completes the (N(2))(2-), (NO)(2-), (O(2))(2-) series with 1 and 3. Specifically, the (µ-O)(2-) oxide-bridged bimetallic complex, [(R(2)N)(2)(THF)Y}(2)(µ-O), 4, is obtained as a byproduct from reactions of either the (N(2))(2-) complex, 1, or the (N(2))(3-) complex, 2, with NO, while the oxide formed from 2 with N(2)O is a polymeric species incorporating potassium, {[(R(2)N)(2)Y](2)(µ-O)(2)K(2)(µ-C(7)H(8))}(n), 5. Reaction of 1 with 1 atm of O(2) generates the (O(2))(2-) bridging side-on peroxide [(R(2)N)(2)(THF)Y](2)(µ-η(2)η(2)-O(2)), 6. The O-O bond in 6 is cleaved by KC(8) to provide an alternative synthetic route to 5. Attempts to oxidize the (NO)(2-) complex, 3, with AgBPh(4) led to the isolation of the tetraphenylborate complex, [(R(2)N)(2)Y(THF)(3)][BPh(4)], 7, that was also synthesized from 1 and AgBPh(4). Oxidation of the (N(2))(2-) complex, 1, with the radical trap (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, TEMPO, generates the (TEMPO)(-) anion complex, (R(2)N)(2)(THF)Y(η(2)-ONC(5)H(6)Me(4)), 8.