Synthesis of the (N2)3- radical from Y2+ and its protonolysis reactivity to form (N2H2)2- via the Y[N(SiMe3)2]3/KC8 reduction system.

Examination of the YN(SiMe(3))(2)/KC(8) reduction system that allowed isolation of the (N(2))(3-) radical has led to the first evidence of Y(2+) in solution. The deep-blue solutions obtained from YN(SiMe(3))(2) and KC(8) in THF at -35 °C under argon have EPR spectra containing a doublet at g(iso) = 1.976 with a 110 G hyperfine coupling constant. The solutions react with N(2) to generate (N(2))(2-) and (N(2))(3-) complexes {(Me(3)Si)(2)N(THF)Y}(2)(μ-η(2):η(2)-N(2)) (1) and {(Me(3)Si)(2)N(THF)Y}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)] (2), respectively, and demonstrate that the YN(SiMe(3))(2)/KC(8) reaction can proceed through an Y(2+) intermediate. The reactivity of (N(2))(3-) radical with proton sources was probed for the first time for comparison with the (N(2))(2-) and (N(2))(4-) chemistry. Complex 2 reacts with [Et(3)NH][BPh(4)] to form {(Me(3)Si)(2)N(THF)Y}(2)(μ-N(2)H(2)), the first lanthanide (N(2)H(2))(2-) complex derived from dinitrogen, as well as 1 as a byproduct, consistent with radical disproportionation reactivity.