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Rhodium(III) and iridium(III) complexes of a NHC-based macrocycle : persistent weak agostic interactions and reactions with dihydrogen
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Gyton, Matthew R., Leforestier, Baptiste and Chaplin, Adrian B. (2018) Rhodium(III) and iridium(III) complexes of a NHC-based macrocycle : persistent weak agostic interactions and reactions with dihydrogen. Organometallics, 37 (21). pp. 3963-3971. doi:10.1021/acs.organomet.8b00595 ISSN 0276-7333.
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Official URL: http://dx.doi.org/10.1021/acs.organomet.8b00595
Abstract
The synthesis and characterization of five-coordinate rhodium(III) and iridium(III) 2,2′-biphenyl complexes [M(CNC-12)(biph)][BArF4] (M = Rh (1a), Ir (1b)), featuring the macrocyclic lutidine- and NHC-based pincer ligand CNC-12 are reported. In the solid state these complexes are notable for the adoption of weak ε-agostic interactions that are characterized by M···H–C contacts of ca. 3.0 Å by X-ray crystallography and ν(CH) bands of reduced wavenumber by ATR IR spectroscopy. Remarkably, these interactions persist on dissolution and were observed at room temperature using NMR spectroscopy (CD2Cl2) and solution-phase IR spectroscopy (CCl4). The associated metrics point toward a stronger M···H–C interaction in the iridium congener, and this conclusion is borne out on interrogation of 1 in silico using DFT-based NBO and QTAIM analyses. Reaction of 1 with dihydrogen resulted in hydrogenolysis of the biaryl and formation of fluxional hydride complexes, whose ground state formulations as [Rh(CNC-12)H2][BArF4] (2a″) and [Ir(CNC-12)H2(H2)][BArF4] (2b‴) are proposed on the basis of inversion recovery and variable-temperature NMR experiments, alongside a computational analysis. Reactions of 1 and 2 with carbon monoxide help support their respective structural properties.
Item Type: | Journal Article | |||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Rhodium compounds, Iridium compounds, Dihydrogen bonding | |||||||||||||||||||||
Journal or Publication Title: | Organometallics | |||||||||||||||||||||
Publisher: | American Chemical Society | |||||||||||||||||||||
ISSN: | 0276-7333 | |||||||||||||||||||||
Official Date: | 12 November 2018 | |||||||||||||||||||||
Dates: |
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Volume: | 37 | |||||||||||||||||||||
Number: | 21 | |||||||||||||||||||||
Page Range: | pp. 3963-3971 | |||||||||||||||||||||
DOI: | 10.1021/acs.organomet.8b00595 | |||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||
Date of first compliant deposit: | 17 October 2018 | |||||||||||||||||||||
Date of first compliant Open Access: | 18 October 2018 | |||||||||||||||||||||
RIOXX Funder/Project Grant: |
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