Dinitrogen Reduction and Functionalization by a Siloxide Supported Thulium-Potassium Complex for the Formation of Ammonia or Hydrazine Derivatives

The dinitrogen (N2) chemistry of lanthanides remains less developed compared to the d-block metals and lanthanide-promoted N2 functionalization chemistry in well-defined lanthanide complexes remains elusive. Here we report the synthesis and characterization (SQUID, EPR, DFT, X-Ray) of the siloxide supported heterobimetallic (Tm/K) complexes [{KTm(OSi(OtBu)3)3}2(μ-η2:η2-N2)] (1) and [K3{Tm(OSi(OtBu)3)3}2(μ-η2:η2-N2)] (2). Complex 2 provides a rare example of a metal complex of the triply reduced N23- radical. The structure of 2 differs from the few previously reported N23- complexes as it presents two Tm and three K cations binding the N23- radical, facilitating N2 functionalization. Notably, the K3Tm2-bound N23- moiety reacts with excess H+ to form NH4Cl in 18% yield, and with MeOTf at room temperature to yield the dimethyl hydrazido complex [K2{Tm(OSi(OtBu)3)3}2(μ-(CH3)NN(CH3))] (3). Protonolysis of 3yields MeHN-NMeH·2HCl in 18 % yield.