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Syntheses, structural characterisation and electronic structures of ferrocenyl-osmafuran heterobinuclear organometallic complexes

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Abstract

The heterobinuclear complex OsCl2(PPh3)2[CHC(PPh3)CFcO] (Fc = (C5H4)Fe(C5H5)) (1) in which the two metal centers were connected by the skeleton of the osmafuran and cyclopentadienyl was synthesized via a one-pot reaction of OsCl2(PPh3)3 and FcCOC[triple bond, length as m-dash]CH in high yield. Three derivatives (Os(η2-OCOO)(PPh3)2[CHC(PPh3)CFcO] (2), Os(NCS)2(PPh3)2[CHC(PPh3)CFcO] (3), and OsCl2(dppb)[CHC(PPh3)CFcO] (dppb = Ph2P(CH2)4PPh2) (4)) were obtained by the ligand substitution reactions of complex 1 with different reagents (Cs2CO3 (2), NaSCN (3) and dppb (4)), respectively. All of these complexes were characterized by NMR spectroscopy and elemental analysis and the structures of complexes 1, 3 and 4 were further confirmed by single crystal X-ray diffraction. Their electrochemical properties were studied by cyclic voltammetry and square wave voltammetry. The first redox wave was ascribed to the couple Os(II)/Os(III). All of these complexes exhibit two redox processes with a large peak separation. However, UV-Vis-NIR combined with theoretical calculation clearly indicated that (1) the Os center plays a major role in the one-electron oxidation process of heterobinuclear complexes 1–4 and the osmafuran could be better described as a carbene ligand; (2) the electronic communication between the Os and Fe center is absent, and the osmafuran with the electron-withdrawing phosphonium substituent actually functioned as an insulating bridge.

Graphical abstract: Syntheses, structural characterisation and electronic structures of ferrocenyl-osmafuran heterobinuclear organometallic complexes

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Publication details

The article was received on 25 Aug 2017, accepted on 17 Oct 2017 and first published on 03 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03145A
Citation: Dalton Trans., 2017, Advance Article
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    Syntheses, structural characterisation and electronic structures of ferrocenyl-osmafuran heterobinuclear organometallic complexes

    B. Liu, C. Guo, W. Liu, Ming-E. Guo, F. Yan, L. Xue, H. Wang, C. Liu and S. Jin, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT03145A

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