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Iron vs. ruthenium: syntheses, structures and IR spectroelectrochemical characterisation of half-sandwich Group 8 acetylide complexes

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Abstract

A convenient modification to the established synthetic routes for the preparation of complexes [M(C[triple bond, length as m-dash]CR)(dppe)Cp′] (M = Fe, Ru; Cp′ = η5-C5H5 (Cp), η5-C5Me5 (Cp*); R = C6H5, C6H4-p-OMe, C6H4-p-NO2, tBu) and [Ru(C[triple bond, length as m-dash]CR)(PPh3)2Cp] from the corresponding [MCl(PP)Cp′] complex and the alkyne HC[triple bond, length as m-dash]CR via an intermediate vinylidene is described. The complexes are generally obtained as high quality crystalline samples directly from the reaction mixture. In agreement with previous studies, the iron complexes undergo a predominantly metal-centred oxidation, whilst there is greater involvement of the acetylide ligand in the oxidation processes associated with the ruthenium analogues. Analysis of the redox properties and spectroelectrochemical investigations reveal limited differences in the gross electronic structures of the Cp vs. Cp* derivatives in each of the Fe and Ru series.

Graphical abstract: Iron vs. ruthenium: syntheses, structures and IR spectroelectrochemical characterisation of half-sandwich Group 8 acetylide complexes

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Article information


Submitted
19 Jun 2020
Accepted
04 Aug 2020
First published
07 Aug 2020

New J. Chem., 2020, Advance Article
Article type
Paper

Iron vs. ruthenium: syntheses, structures and IR spectroelectrochemical characterisation of half-sandwich Group 8 acetylide complexes

D. P. Harrison, V. J. Kumar, J. N. Noppers, J. B. G. Gluyas, A. N. Sobolev, S. A. Moggach and P. J. Low, New J. Chem., 2020, Advance Article , DOI: 10.1039/D0NJ03093G

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