Details

Autor(en) / Beteiligte

• van de Watering, Fenna F.
• Stroek, Wowa
• Ivar van der Vlugt, Jarl
• de Bruin, Bas
• Dzik, Wojciech I.
• Reek, Joost N. H.

Titel

Coordination of 3‐Methylindole‐Based Tripodal Tetraphosphine Ligands to Iron(+II), Cobalt(+II), and Nickel(+II) and Investigations of their Subsequent Two‐Electron Reduction

Ist Teil von

• European journal of inorganic chemistry, 2018-03, Vol.2018 (11), p.1254-1265

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Link zum Volltext

Quelle

Wiley Blackwell Single Titles

Beschreibungen/Notizen

• We report the coordination chemistry of indole based tripodal tetraphosphine ligands to iron(II), cobalt(II) and nickel(II). These complexes are formed by simple synthetic protocols and were characterized by a combination of spectroscopic techniques and single‐crystal X‐ray analysis. The molecular structures as determined by X‐ray diffraction show that the geometry of the nickel and cobalt complexes are distorted trigonal bipyramidal. The monocationic iron(II) complexes also have distorted trigonal bipyramidal geometries, but the dicationic analogue has an octahedral geometry. Two‐electron reduction of the cobalt(+II) and the nickel(+II) complexes in the presence of N2 did not lead to the coordination of N2. In contrast, two‐electron reduction of the iron(+II) complexes did lead to coordination of dinitrogen to the iron center. The Fe0N2L1H complex has a trigonal bipyramidal geometry, and the N–N bond length of the coordinated dinitrogen ligand is longer than that of free dinitrogen, indicating that coordination to this iron(0) complex results in activation of the N≡N bond. FeN2 and chlorido complexes of iron(II), cobalt(II) and nickel(II) with indole based tripodal tetraphosphine ligands are reported. Two‐electron reduction of the cobalt(+II) and the nickel(+II) complex in the presence of N2 did not lead to the coordination of N2, whereas those complexes based on iron(+II) were formed.