Related Experiment Video
Updated: Jun 10, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Dinitrogen Reduction and Functionalization by a Siloxide Supported Thulium-Potassium Complex for the Formation of
R A Keerthi Shivaraam1, Thayalan Rajeshkumar2, Rosario Scopelliti3
1Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Abstract:
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 N2 3- radical. The structure of 2 differs from the few previously reported N2 3- complexes as it presents two Tm and three K cations binding the N2 3- radical, facilitating N2 functionalization. Notably, the K3Tm2-bound N2 3- 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 3 yields MeHN-NMeH ⋅ 2HCl in 18 % yield.
More Related Videos
Related Concept Videos
Nitriles to Amines: LiAlH4 Reduction
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Preparation of Amines: Reduction of Amides and Nitriles
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...
Preparation of Amines: Reduction of Oximes and Nitro Compounds
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Preparation of Nitriles
Preparation of Amines: Reductive Amination of Aldehydes and Ketones

