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Half-Sandwich Complexes of an Extremely Electron-Donating, Re-dox-Active η\(^6\)-Diborabenzene Ligand

Please always quote using this URN: urn:nbn:de:bvb:20-opus-156766
  • 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.show moreshow less

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Metadaten
Author: Julian Böhnke, Holger BraunschweigORCiD, Oscar Jiménez-Halla, Ivo Krummenacher, Tom E. Stennett
URN:urn:nbn:de:bvb:20-opus-156766
Document Type:Preprint
Faculties:Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie
Language:English
Parent Title (English):Journal of the American Chemical Society
Year of Completion:2018
Source: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
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie
Tag:boron; half-sandwich complexes; redox reactions; transition metal complex
Release Date:2018/01/19
EU-Project number / Contract (GA) number:669054
OpenAIRE:OpenAIRE
Note:
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.
Licence (German):License LogoDeutsches Urheberrecht