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Oxidative addition of C–Cl bonds to a Rh(PONOP) pincer complex
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Longcake, Alexandra, Lees, Martin R., Senn, Mark S. and Chaplin, Adrian B. (2022) Oxidative addition of C–Cl bonds to a Rh(PONOP) pincer complex. Organometallics, 41 (23). pp. 3557-3567. doi:10.1021/acs.organomet.2c00400 ISSN 0276-7333.
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WRAP-Oxidative-addition-C–Cl-bonds-RhPONOP-pincer-complex-22.pdf - Accepted Version Embargoed item. Restricted access to Repository staff only - Requires a PDF viewer. Download (3259Kb) |
Official URL: https://doi.org/10.1021/acs.organomet.2c00400
Abstract
Straightforward procedures for the generation of rhodium(I) κCl–chlorocarbon complexes of the form [Rh(PONOP-tBu)(κCl–ClR)][BArF4] [R = CH2Cl, A; Ph, 1; Cy, 2; tBu, 3; PONOP-tBu = 2,6-bis(di-tert-butylphosphinito)pyridine; ArF = 3,5-bis(trifluoromethyl)phenyl] in solution are described, enabling isolation of analytically pure A and crystallographic characterization of the new complexes 1 and 2. Complex 1 was found to be stable at ambient temperature, but prolonged heating in chlorobenzene at 125 °C resulted in formation of [Rh(PONOP-tBu)(Ph)Cl][BArF4] 4 with experimental and literature evidence pointing toward a concerted C(sp2)–Cl bond oxidative addition mechanism. C(sp3)–Cl bond activation of dichloromethane, chlorocyclohexane, and 2-chloro-2-methylpropane by the rhodium(I) pincer occurred under considerably milder conditions, and radical mechanisms that commence with chloride atom abstraction and involve generation of the rhodium(II) metalloradical [Rh(PONOP-tBu)Cl][BArF4] 6 are instead proposed. For dichloromethane, [Rh(PONOP-tBu)(CH2Cl)Cl][BArF4] 5 was formed in the dark, but facile photo-induced reductive elimination occurred when exposed to light. Net dehydrochlorination affording [Rh(PONOP-tBu)(H)Cl][BArF4] 7 and an alkene byproduct resulted for chlorocyclohexane and 2-chloro-2-methylpropane, consistent with hydrogen atom abstraction from the corresponding alkyl radicals by 6. This suggestion is supported by dynamic hydrogen atom transfer between 6 and 7 on the 1H NMR time scale at 298 K in the presence of TEMPO.
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, Ligands (Biochemistry) -- Research, Catalysis, Organometallic chemistry -- Research | |||||||||
Journal or Publication Title: | Organometallics | |||||||||
Publisher: | American Chemical Society | |||||||||
ISSN: | 0276-7333 | |||||||||
Official Date: | 12 December 2022 | |||||||||
Dates: |
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Volume: | 41 | |||||||||
Number: | 23 | |||||||||
Page Range: | pp. 3557-3567 | |||||||||
DOI: | 10.1021/acs.organomet.2c00400 | |||||||||
Status: | Peer Reviewed | |||||||||
Publication Status: | Published | |||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||
Date of first compliant deposit: | 30 September 2022 | |||||||||
Date of first compliant Open Access: | 1 November 2022 | |||||||||
RIOXX Funder/Project Grant: |
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