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Metal–Metal Interaction in Fischer Carbene Complexes: A Study of Ferrocenyl and Biferrocenyl Tungsten Alkylidene Complexes

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† Chemistry Department, University of Pretoria, Private Bag X20, Hatfield 0028, South Africa
‡ Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, Technische Universität Chemnitz, D-09107 Chemnitz, Germany
§ Fakultät für Naturwissenschaften, Institut für Chemie, Theoretische Chemie, Technische Universität Chemnitz, D-09107 Chemnitz, Germany
*(D.I.B.) E-mail: [email protected]; phone: +27-(0)12-420-2626; fax.: +27-(0)12-420-4687.
*(H.L.) E-mail: [email protected]; phone: +49 (0)371-531-21210; fax.: +49 (0)371-531-21219.
Cite this: Inorg. Chem. 2013, 52, 24, 14253–14263
Publication Date (Web):December 3, 2013
https://doi.org/10.1021/ic402202w
Copyright © 2013 American Chemical Society
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Abstract

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A series of ferrocenyl (Fc = ferrocenyl; fc = ferrocen-1,1′-diyl) and biferrocenyl (Bfc = 1′,1″-biferrocenyl; bfc = 1′,1″-biferrocen-1,1‴-diyl) mono- and biscarbene tungsten(0) complexes of the type [(CO)5W═C(OMe)R] (1, R = Fc; 3, R = Bfc) and [(CO)5W═C(OMe)-R′-(OMe)C═W(CO)5] (2, R′ = fc; 4, R′ = bfc) were synthesized according to the classical synthetic methodology by reacting W(CO)6 with LiR (R = Fc, fc, bfc), followed by a subsequent alkylation using methyl trifluoromethanesulfonate. Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1–4. The ferrocenyl and biferrocenyl moieties in 1–4 show reversible one-electron redox events. It was further found that the Fischer carbene unit is reducible in an electrochemical one-electron transfer process. For the tungsten carbonyl moieties, irreversible oxidation processes were found. In addition, charge transfer studies were performed on 1–4 using in situ UV–vis-NIR and infrared spectroelectrochemical techniques. During the UV–vis-NIR investigations, typical low energy transitions for the mixed-valent biferrocenyl unit were found. A further observed high energy NIR absorption is attributed to a metal–metal charge transfer transition between the tungsten carbonyl fragment and the ferrocenyl/biferrocenyl group in the corresponding oxidized states, which can be described as class II systems according to Robin and Day. This assignment was verified by infrared spectroelectrochemical studies. The electrochemical investigations are supported by density functional theory calculations. The structural properties of 1–4 in the solid state were investigated by single-crystal X-ray diffraction studies showing no substituent effects on bond lengths and angles. The biferrocenyl derivatives exhibit syn-conformation of the ferrocenyl and carbene building blocks.

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UV–vis/NIR spectra in dichloromethane and crystal structure details for 1–4 as well as calculated infrared spectra of 1 and 1+ are given. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

This article is cited by 17 publications.

  1. Hana Váňová, Tomáš Tobrman, Irena Hoskovcová, and Dalimil Dvořák . Modular Synthesis of Fischer Biscarbene Complexes of Chromium. Organometallics 2016, 35 (17) , 2999-3006. https://doi.org/10.1021/acs.organomet.6b00527
  2. J. Matthäus Speck, Marcus Korb, Alexander Schade, Stefan Spange, and Heinrich Lang . Ferrocenes Bridged by Ethylenediamino Thiophene: Varying Charge Transfer Properties in a Series of 3,4-Di-N-substituted 2,5-Diferrocenyl Thiophenes. Organometallics 2015, 34 (15) , 3788-3798. https://doi.org/10.1021/acs.organomet.5b00450
  3. Tei Tagg, Henrik G. Kjaergaard, Joseph R. Lane, C. John McAdam, Brian H. Robinson, and Jim Simpson . Unusual Low-Energy Near-Infrared Bands for Ferrocenyl–Naphthalimide Donor–Acceptor Dyads with Aromatic Spacer Groups: Prediction by Time-Dependent DFT and Observation by OTTLE Spectroscopy. Organometallics 2015, 34 (11) , 2662-2666. https://doi.org/10.1021/om501315k
  4. J. Matthäus Speck, Marcus Korb, Tobias Rüffer, Alexander Hildebrandt, and Heinrich Lang . Substituent Influence on Charge Transfer Interactions in α,α′-Diferrocenylthiophenes. Organometallics 2014, 33 (18) , 4813-4823. https://doi.org/10.1021/om500062h
  5. Nora‐ann Weststrate, Christopher Hassenrück, Michael Linseis, David C. Liles, Simon Lotz, Helmar Görls, Rainer F. Winter. The Effect of Remote Donor Substituents on the Properties of Alkoxy and Amino Fischer Carbene Complexes of Tungsten. Zeitschrift für anorganische und allgemeine Chemie 2021, 56 https://doi.org/10.1002/zaac.202100081
  6. Dominique Gottwald, Qing Yuan, Matthäus Speck, Julia Mahrholdt, Marcus Korb, Katja Schreiter, Stefan Spange, Heinrich Lang. Synthesis and (spectro)electrochemistry of 1′,1′′′-disubstituted biferrocenes. Journal of Organometallic Chemistry 2020, 923 , 121447. https://doi.org/10.1016/j.jorganchem.2020.121447
  7. Hana Váňová, Tomáš Tobrman, Martin Babor, Dalimil Dvořák. Reaction of lithiated thiophene-derived aminocarbene complexes with inorganic halides: Preparation of a heteroatom containing mono- and multicarbene complexes. Journal of Organometallic Chemistry 2019, 882 , 90-95. https://doi.org/10.1016/j.jorganchem.2018.12.015
  8. J. Matthäus Speck, Marcus Korb, Alexander Hildebrandt, Heinrich Lang. Ferrocenyl-Functionalized η 5 -Thiophene Cr(CO) 3 Half-Sandwich Compounds. European Journal of Inorganic Chemistry 2018, 2018 (41) , 4566-4572. https://doi.org/10.1002/ejic.201800749
  9. Deeb Taher, Firas F. Awwadi, J. Matthäus Speck, Marcus Korb, Dieter Schaarschmidt, Saddam Weheabby, Almeqdad Y. Habashneh, Mousa Al-Noaimi, Mohammad El-Khateeb, Sultan T. Abu-Orabi, Heinrich Lang. Heterocyclic-based ferrocenyl carboselenolates: Synthesis, solid-state structure and electrochemical investigations. Journal of Organometallic Chemistry 2017, 845 , 55-62. https://doi.org/10.1016/j.jorganchem.2017.02.024
  10. Danielle Aucamp, Tim Witteler, Fabian Dielmann, Shepherd Siangwata, David C. Liles, Gregory S. Smith, Daniela I. Bezuidenhout. A Triarylated 1,2,3-Triazol-5-ylidene Ligand with a Redox-Active Ferrocenyl Substituent for Rhodium(I)-Catalyzed Hydroformylation of 1-Octene. European Journal of Inorganic Chemistry 2017, 2017 (9) , 1227-1236. https://doi.org/10.1002/ejic.201700164
  11. Zandria Lamprecht, Shankara G. Radhakrishnan, Alexander Hildebrandt, Heinrich Lang, David C. Liles, Nora-ann Weststrate, Simon Lotz, Daniela I. Bezuidenhout. Mono-, di- and tetrarhenium Fischer carbene complexes with thienothiophene substituents. Dalton Trans. 2017, 46 (40) , 13983-13993. https://doi.org/10.1039/C7DT02969A
  12. Philipp Veit, Christoph Förster, Katja Heinze. On the mechanism of imine elimination from Fischer tungsten carbene complexes. Beilstein Journal of Organic Chemistry 2016, 12 , 1322-1333. https://doi.org/10.3762/bjoc.12.125
  13. Philipp Veit, Christoph Förster, Sebastian Seibert, Katja Heinze. Preparation, Properties, and Reactivity of (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)chromium(0) as Bulky Isolobal Trimetallo-amide. Zeitschrift für anorganische und allgemeine Chemie 2015, 641 (12-13) , 2083-2092. https://doi.org/10.1002/zaac.201500562
  14. James W. Herndon. The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2013. Coordination Chemistry Reviews 2015, 286 , 30-150. https://doi.org/10.1016/j.ccr.2014.09.021
  15. Marilé Landman, Blenerhassitt E. Buitendach, Marrigje M. Conradie, Roan Fraser, Petrus H. van Rooyen, Jeanet Conradie. Fischer mono- and biscarbene complexes of tungsten with mono- and dimeric heteroaromatic substituents. Journal of Electroanalytical Chemistry 2015, 739 , 202-210. https://doi.org/10.1016/j.jelechem.2014.12.019
  16. Belinda van der Westhuizen, J. Matthäus Speck, Marcus Korb, Daniela I. Bezuidenhout, Heinrich Lang. (Spectro)electrochemical investigations on (ferrocenyl)thiophenes modified by tungsten Fischer carbenes. Journal of Organometallic Chemistry 2014, 772-773 , 18-26. https://doi.org/10.1016/j.jorganchem.2014.08.025
  17. Daniela I. Bezuidenhout, Belinda van der Westhuizen, Ian Strydom, Pieter J. Swarts, Jannie C. Swarts, Israel Fernández. Synthesis and electrochemical investigation of chromium(0) ferrocenyl-substituted carbene complexes. Inorganica Chimica Acta 2014, 423 , 184-192. https://doi.org/10.1016/j.ica.2014.07.068

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