Oxygen-atom transfer from nitrous oxide. Synthesis and structure of a zirconocene oxametallacyclobutene complex

N2O Reduction by the μ4‐Sulfide‐Bridged Tetranuclear CuZ Cluster Active Site

“…[3] Reduction of N 2 O in homogenous systems normally requires transition metals, such as Ti, V, Ni, Zr, Ru, Hf, [4][5][6][7][8][9] as activation centers, where the required two electrons are either derived from the metal centers, which results in terminal [10,11] or bridged [4] metal-oxide products, or from the ligands through insertion of the oxygen atom into the metal-ligand bond. [5][6][7]12] To date, none of the reported metal/N 2 O complexes has been structurally determined crystallographically. The N 2 O unit in the [(NH 3 ) 5 Ru(N 2 O)] 2+ complex has been found from spectroscopy to coordinate to the ruthenium atom in a linear end-on mode by its terminal nitrogen atom.…”

“…[5][6][7]12] To date, none of the reported metal/N 2 O complexes has been structurally determined crystallographically. The N 2 O unit in the [(NH 3 ) 5 Ru(N 2 O)] 2+ complex has been found from spectroscopy to coordinate to the ruthenium atom in a linear end-on mode by its terminal nitrogen atom. [13] Additional terminal oxygen coordination to metal sites has also been implicated in the formation of the {Ru(N 2 O)Ru} dimer [10,14] and has been spectroscopically identified in N 2 O adsorption on a-Cr 2 O 3 .…”

Preparation, Characterization, and Aquation Kinetics of Pyridine N‐Oxide Complexes of Chromium(III)

“…Often, although not always, [6] such reactions involve oxygen-atom transfer [7][8][9] with pyridine N-oxide playing a role of either oxygen-atom donor [2,[7][8][9][10][11][12] or a promoter of oxygen transfer from active donors to the substrate. [13][14][15][16] Metal catalysis is frequently involved [17] in such processes, which makes mechanistic studies of transition-metal complexes of pyridine N-oxides an important area of investigation.…”

“…Prior to this work, only the parent ion, (H 2 O) 5 Cr(pyO) 3+ , was known. [24] It was generated by thermal equilibration of Cr(H 2 O) 6 3+ with an excess of pyO in slightly acidic aqueous solutions at elevated temperatures, followed by ion exchange. In the present work, our previously published procedure for the preparation of pyridine chromium complexes [22] was applied to pyridine N-oxide analogues.…”

Reduktion von N2O an einem μ4‐sulfidverbrückten vierkernigen aktiven CuZ‐Zentrum

“…[3] Für eine erfolgreiche Reduktion muss N 2 O in homogenen Systemen normalerweise zunächst durch Übergangs-metalle wie Ti, V, Ni, Zr, Ru oder Hf aktiviert werden. [4][5][6][7][8][9] Die beiden dazu benötigten Elektronen stammen entweder vom Metallzentrum (Bildung endständiger [10,11] oder verbrückter [4] Metalloxide) oder von den Liganden (Insertion des Sauerstoffatoms in die Metall-Ligand-Bindung [5][6][7]12] -Komplexkations ergaben eine lineare End-on-Koordination von N 2 O über sein endständiges Stickstoffatom an das Rutheniumzentrum. [13] Im dimeren {Ru(N 2 O)Ru}-Komplex wird eine zusätzliche Koordination durch das terminale Sauerstoffatom von N 2 O an das zweite Metallzentrum angenommen; [10,14] im Falle der N 2 OAdsorption an a-Cr 2 O 3 wurde eine solche Koordination spektroskopisch nachgewiesen.…”