Related Experiment Video
Updated: Apr 26, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Two-electron reductive carbonylation of terminal uranium(V) and uranium(VI) nitrides to cyanate by carbon monoxide
Peter A Cleaves1, David M King, Christos E Kefalidis
1School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
Abstract:
Two-electron reductive carbonylation of the uranium(VI) nitride [U(Tren(TIPS))(N)] (2, Tren(TIPS)=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(Tren(TIPS))(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(Tren(TIPS))] (4) and KNCO, or cyanate retention in [U(Tren(TIPS))(NCO)][K(B15C5)2] (5, B15C5=benzo-15-crown-5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(Tren(TIPS))(N)K}2] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(Tren(TIPS))(N)][K(B15C5)2] (7). Notably, 7 reacts with CO much faster than 2. This unprecedented f-block reactivity was modeled theoretically, revealing nucleophilic attack of the π* orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcal mol(-1) for uranium(VI) and uranium(V), respectively. A remarkably simple two-step, two-electron cycle for the conversion of azide to nitride to cyanate using 4, NaN3 and CO is presented.
More Related Videos
12:05U2O5 Film Preparation via UO2 Deposition by Direct Current Sputtering and Successive Oxidation and Reduction with Atomic Oxygen and Atomic Hydrogen
Published on: February 21, 2019
07:36Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Related Concept Videos
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Preparation of Nitriles
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
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...
Nitrosation of Enols