Oxidative Dehydrogenation of Secondary Amines: The Case of the N,N,N′‐Tris(2‐pyridylmethyl)‐o‐phenylenediamine Ligand when Coordinated to Iron Dichloride

Abstract

We report the preparation and the X-ray crystal structure of

The Coordination Chemistry of FeCl3 and FeCl2 to Bis[2‐(2,3‐dihydroxyphenyl)‐6‐pyridylmethyl](2‐pyridylmethyl)amine: Access to a Diiron(III) Compound with an Unusual Pentagonal‐Bipyramidal/Square‐Pyramidal Environment

“…[19] We have been involved in the chemistry of stable iron(ii) derivatives with various substituted aminomethylpyridylcontaining ligands, and have reported that some of them exhibit an interesting reactivity towards dioxygen. [20][21][22] As an extension of our work with substituted TPA derivatives, we decided to prepare a ligand with two very different coordination sites, namely bis[2-(2,3-dihydroxyphenyl)-6-pyridylmethyl](2-pyridylmethyl)amine (BCATTPA), whose structure is shown in Scheme 1, and embarked upon an investigation of the coordination chemistry of this ligand with iron-A C H T U N G T R E N N U N G (iii) and iron(ii) chloride.…”

C–H benzylic oxidation promoted by dinuclear iron DBDOC iminopyridine complexes

“…For example, complex 8 containing the amino derivative was the worst catalyst for this transformation with only 20% yield (entry 3). It is known from literature that secondary amines can be oxidized in the presence of iron and oxidant [29,30], thus they are less stable than imine complexes and the conversion decreased for these ligands.…”

Oxidative Dehydrogenation of Hexaaza Macrocyclic Nickel(II) Complexes Bearing Two N-Alkyl Pendant Arms: Preparation of New Complexes Containing Imidoylamidine Linkages

“…Figure 1 shows that the cation 1 has a square-planar coordination polyhedron with an inversion center at the metal ion and a two-fold rotational axis through the midpoint of the ethylene group in each fivemembered chelate ring. The ClO 4 − anion is not involved in coordination. Two phenyl groups of 1 are anti with respect to the macrocyclic plane.…”

“…7 Literature up to date clearly shows that the number and position of the imino groups in the product is strongly influenced by the structural characteristics of the macrocycle. [3][4][5][6][7][8][9] In this work, we attempted the oxidative dehydrogenation of the hexaaza macrocyclic complexes [ ](ClO 4 ) 2 were prepared as described previously. 14,15 Infrared spectra were recorded with a Shimadzu IR-440 spectrophotometer, electronic absorption spectra with an Analytikjena Specord 200 UV/Vis spectrophotometer, 13 C-NMR spectra with a Varian Mercury 300 NMR spectrometer, and conductance measurements with a Metrohm Herisau Conductometer E518.…”

“…Cyclic voltammograms were recorded using a BAS-100 B/W auto cyclic volt/ampere meter. The electrochemical measurements were conducted in 0.1 M (nBu) 4 formed was removed by filtration, and water (10 mL) was added to the filtrate. A yellow solid was filtered, washed with water, and dried in air.…”