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Functionalization of Rh^(III)–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Gu, Shunyan and Chen, Junqi and Musgrave, Charles B., III and Gehman, Zoë M. and Habgood, Laurel G. and Jia, Xiaofan and Dickie, Diane A. and Goddard, William A., III and Gunnoe, T. Brent (2021) Functionalization of Rh^(III)–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination. Organometallics, 40 (12). pp. 1889-1906. ISSN 0276-7333. doi:10.1021/acs.organomet.1c00223.

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We show how to improve the yield of MeX from CH₄ activation catalysts from 12% to 90% through the use of “capping arene” ligands. Four (FP)Rh^(III)(Me)(TFA)₂ {FP = “capping arene” ligands, including 8,8′-(1,2-phenylene)diquinoline (6-FP), 8,8′-(1,2-naphthalene)diquinoline (6-^(NP)FP), 1,2-bis(N-7-azaindolyl)benzene (5-FP), and 1,2-bis(N-7-azaindolyl)naphthalene (5-^(NP)FP)} complexes. These complexes and (dpe)Rh^(III)(Me)(TFA)₂ (dpe = 1,2-di-2-pyridylethane) were synthesized and tested for their performance in reductive elimination of MeX (X = TFA or halide). The FP ligands were used with the goal of blocking a coordination site to destabilize the Rh^(III) complexes and facilitate MeX reductive elimination. On the basis of single-crystal X-ray diffraction studies, the 6-FP and 6-^(NP)FP ligated Rh complexes have Rh–arene distances shorter than those of the 5-FP and 5-^(NP)FP Rh complexes; thus, it is expected that the Rh–arene interactions are weaker for the 5-FP complexes than for the 6-FP complexes. Consistent with our hypothesis, the 5-FP and 5-^(NP)FP Rh^(III) complexes demonstrate improved performance (from 12% to ∼60% yield) in the reductive elimination of MeX. The reductive elimination of MeX from (FP)Rh^(III)(Me)(TFA)₂ can be further improved by the use of chemical oxidants. For example, the addition of 2 equiv of AgOTf leads to 87(2)% yield of MeTFA and can be achieved in CD₃CN at 90 °C using (5-FP)Rh(Me)(TFA)₂.

Item Type:Article
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URLURL TypeDescription
Gu, Shunyan0000-0002-3625-1042
Musgrave, Charles B., III0000-0002-3432-0817
Habgood, Laurel G.0000-0001-5475-1561
Jia, Xiaofan0000-0003-0425-5089
Dickie, Diane A.0000-0003-0939-3309
Goddard, William A., III0000-0003-0097-5716
Gunnoe, T. Brent0000-0001-5714-3887
Alternate Title:Functionalization of RhIII–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination
Additional Information:© 2021 American Chemical Society. Received: April 8, 2021. The Gunnoe group acknowledges support from the U.S. National Science Foundation (1800173). C.B.M. and W.A.G. acknowledge support from the NSF (CBET-1805022). Single-crystal X-ray diffraction experiments were performed on a diffractometer at the University of Virginia funded by the NSF-MRI program (CHE-2018870). Accession Codes: CCDC 2046421–2046427, 2046429–2046432, and 2068537 contains the supplementary crystallographic data for this paper. Author Contributions: S.G. and J.C. contributed equally to this work. The authors declare no competing financial interest.
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Subject Keywords:Functionalization, Hydrocarbons, Ligands, Reductive elimination, Elimination reactions
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Issue or Number:12
Record Number:CaltechAUTHORS:20210511-093624636
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Official Citation:Functionalization of RhIII–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination. Shunyan Gu, Junqi Chen, Charles B. Musgrave, Zoë M. Gehman, Laurel G. Habgood, Xiaofan Jia, Diane A. Dickie, William A. Goddard, and T. Brent Gunnoe. Organometallics 2021 40 (12), 1889-1906; DOI: 10.1021/acs.organomet.1c00223
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109074
Deposited By: Tony Diaz
Deposited On:11 May 2021 21:50
Last Modified:06 Jul 2021 19:26

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