Issue 7, 2000

A monometallic and kinetically inert complex of a ditopic open ligand as a tight polyaza cage

Abstract

The new ligand L has been prepared by appending three 2,2′-bipyridine molecules to a tren (tris(2-aminoethyl)amine) unit. It binds a Fe2+ cation with its three bipyridines, imparting to it an octahedral co-ordination. The obtained [FeL]2+ molecular cation has a closed shape, whose nature has been ascertained by X-ray diffraction studies on the complex [Fe(HL)][PF6]3. The tren unit can thus be described as one half of a bis-tren cage. The kinetic inertness of the complex between Fe2+ and the three bipyridines has been verified: in the pH 2–12 range the [FeII(bipyR)3] unit is stable and plays only an architectural role. According to this it has been possible to determine the protonation and complexation constants (in the presence of 1 equivalent of Cu2+) of the tren fragment, which is in fact able to interact with protons and metal cations, behaving as a tight and rigid half of a bis-tren ligand. High percentages (70–100%) of the [FeLHn](n + 2)+ species can be found in sharp pH ranges, while, in the presence of 1 equivalent of Cu2+, the metal-containing species [FeCu(HL)]5+, [FeCuL]4+, [FeCuL(OH)]3+ and [FeCuL(OH)2]2+ exist in the pH 2–12 range, each one prevailing in distinct pH intervals, reaching high percentages (70–100%). The variation of the spectral and electrochemical properties of the [Fe(bipyR)3] fragment have been studied as a function of pH, and related with the protonation degree or complexation of the tren unit.

Supplementary files

Article information

Article type
Paper
Submitted
13 Dec 1999
Accepted
14 Feb 2000
First published
20 Mar 2000

J. Chem. Soc., Dalton Trans., 2000, 1155-1160

A monometallic and kinetically inert complex of a ditopic open ligand as a tight polyaza cage

V. Amendola, L. Fabbrizzi, C. Mangano, A. M. Lanfredi, P. Pallavicini, A. Perotti and F. Ugozzoli, J. Chem. Soc., Dalton Trans., 2000, 1155 DOI: 10.1039/A909756B

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