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Half-Sandwich Complexes of an Extremely Electron-Donating, Re-dox-Active η\(^6\)-Diborabenzene Ligand
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- The heteroarene 1,4-bis(CAAC)-1,4-diborabenzene (1; CAAC = cyclic (alkyl)(amino)carbene) reacts with [(MeCN)\(_3\)M(CO)\(_3\)] (M = Cr, Mo, W) to yield half-sandwich complexes of the form [(η\(^6\)-diborabenzene)M(CO)\(_3\)] (M = Cr (2), Mo (3), W (4)). Investigation of the new complexes with a combination of X-ray diffraction, spectroscopic methods and DFT calculations shows that ligand 1 is a remarkably strong electron donor. In particular, [(η\(^6\)-arene)M(CO)\(_3\)] complexes of this ligand display the lowest CO stretching frequencies yetThe heteroarene 1,4-bis(CAAC)-1,4-diborabenzene (1; CAAC = cyclic (alkyl)(amino)carbene) reacts with [(MeCN)\(_3\)M(CO)\(_3\)] (M = Cr, Mo, W) to yield half-sandwich complexes of the form [(η\(^6\)-diborabenzene)M(CO)\(_3\)] (M = Cr (2), Mo (3), W (4)). Investigation of the new complexes with a combination of X-ray diffraction, spectroscopic methods and DFT calculations shows that ligand 1 is a remarkably strong electron donor. In particular, [(η\(^6\)-arene)M(CO)\(_3\)] complexes of this ligand display the lowest CO stretching frequencies yet observed for this class of complex. Cyclic voltammetry on complexes 2-4 revealed one reversi- ble oxidation and two reversible reduction events in each case, with no evidence of ring-slippage of the arene to the η\(^4\) binding mode. Treatment of 4 with lithium metal in THF led to identification of the paramagnetic complex [(1)W(CO)\(_3\)]Li·2THF (5). Compound 1 can also be reduced in the absence of a transition metal to its dianion 1\(^{2–}\), which possesses a quinoid-type structure.…
Autor(en): | Julian Böhnke, Holger BraunschweigORCiD, Oscar Jiménez-Halla, Ivo Krummenacher, Tom E. Stennett |
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URN: | urn:nbn:de:bvb:20-opus-156766 |
Dokumentart: | Preprint (Vorabdruck) |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Journal of the American Chemical Society |
Erscheinungsjahr: | 2018 |
Originalveröffentlichung / Quelle: | Journal of the American Chemical Society, 2018, 140 (2), pp 848–853 DOI: 10.1021/jacs.7b12394 |
DOI: | https://doi.org/10.1021/jacs.7b12394 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Freie Schlagwort(e): | boron; half-sandwich complexes; redox reactions; transition metal complex |
Datum der Freischaltung: | 19.01.2018 |
EU-Projektnummer / Contract (GA) number: | 669054 |
OpenAIRE: | OpenAIRE |
Anmerkungen: | This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © 2017 American Chemical Society after peer review. To access the final edited and published work see dx.doi.org/10.1021/jacs.7b12394. |
Lizenz (Deutsch): | Deutsches Urheberrecht |