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Issue 16, 2014
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Role of basic sites of substituted ferrocenes in interaction with the trinuclear 3,5-bis(trifluoromethyl)pyrazolates: thermodynamics and structure of complexes

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Abstract

Formation of complexes of the macrocycles (ML)3, where L = 3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate, M = Cu and Ag, and the acylferrocenes FcC(O)CH2R (Fc = (C5H5)Fe(C5H4); R = H (1), Ph (2)) was studied by means of variable temperature IR, UV-vis, NMR spectroscopy. The sole site of coordination in solution is the oxygen atom of the CO group. The complex composition (1 : 1) and thermodynamic parameters in hexane solution were determined, the formation constants and the enthalpies decreasing from 1 to 2 and from Ag to the Cu macrocycle. The same coordination site featuring triple coordination of oxygen to all metal atoms of a macrocycle was found in the solid state by single crystal X-ray diffraction. There are no shortened contacts of the metal in the macrocycles with π-electron system of the ferrocene's cyclopentadienyl ligands in all complexes. The complexes of (ML)3 with 1 have 1 : 2 composition and bipyramidal structure whereas 2 forms the 1 : 1 complex with (AgL)3. The latter is packed in the infinite stacks involving additional contacts with Ph groups.

Graphical abstract: Role of basic sites of substituted ferrocenes in interaction with the trinuclear 3,5-bis(trifluoromethyl)pyrazolates: thermodynamics and structure of complexes

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Article information


Submitted
26 Nov 2013
Accepted
13 Jan 2014
First published
14 Jan 2014

RSC Adv., 2014,4, 8350-8359
Article type
Paper

Role of basic sites of substituted ferrocenes in interaction with the trinuclear 3,5-bis(trifluoromethyl)pyrazolates: thermodynamics and structure of complexes

A. A. Titov, O. A. Filippov, E. A. Guseva, A. F. Smol'yakov, F. M. Dolgushin, L. M. Epstein, V. K. Belsky and E. S. Shubina, RSC Adv., 2014, 4, 8350
DOI: 10.1039/C3RA47040G

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