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

Daniel P. Harrison, Varshini Jayantha Kumar, Jo Noppers, Josef Gluyas, Alexandre Sobolev, Stephen Moggach, Paul Low

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)14932-14943
Number of pages12
JournalNew Journal of Chemistry: a journal for new directions in chemistry
Volume45
Issue number33
Early online date7 Aug 2020
DOIs
Publication statusPublished - 7 Sept 2021

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