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(O<italic>t</italic>Bu)3)3}2(<italic>μ</italic>‐<italic>η</italic>2 : <italic>η</italic>2‐N2)] (<bold>1</bold>) and [K3{Tm(OSi(O<italic>t</italic>Bu)3)3}2(<italic>μ</italic>‐<italic>η</italic>2 : <italic>η</italic>2‐N2)] (<bold>2</bold>). Complex <bold>2</bold> provides a rare example of a metal complex of the triply reduced N23− radical. The structure of <bold>2</bold> 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(O<italic>t</italic>Bu)3)3}2(<italic>μ</italic>‐(CH3)NN(CH3))] (<bold>3</bold>). Protonolysis of <bold>3</bold> yields MeHN−NMeH ⋅ 2HCl in 18 % yield. [ABSTRACT FROM AUTHOR]