Direct observation of beta-aryl eliminations from Rh(I) alkoxides

Journal of the American Chemical Society
Pinjing ZhaoJohn F Hartwig

Abstract

beta-Aryl eliminations from a series of rhodium(I) alkoxides to form rhodium aryl complexes and free ketones are reported. Tertiary phenylmethoxide complexes [Rh(PEt3)n(OCPhRR')] (n = 2, 3) were prepared via alcoholysis of {Rh(PEt3)2[N(SiMe3)2} by the corresponding alcohols HOCPhRR' in the presence and absence of added PEt3. Heating of these complexes in the presence of added PEt3 generated the rhodium phenyl complex, (PEt3)3RhPh, and the corresponding ketones in good to high yields. Kinetic results are most consistent with irreversible beta-phenyl elimination from a bisphosphine-ligated rhodium alkoxide complex. Such bisphosphine complexes result from ligand dissociation from the trisphosphine complexes and have been isolated in some cases. The bisphosphine complexes are stabilized by Rh-Cphenyl interactions, as evidenced by an X-ray structure, and this structure with a metal-aryl interaction likely illustrates the pathway for C-C bond cleavage.

References

Oct 18, 2001·Journal of the American Chemical Society·Y TeraoM Nomura
Apr 1, 2004·Angewandte Chemie·Wolfgang Scherer, G Sean McGrady
Aug 18, 2005·Journal of the American Chemical Society·Pinjing Zhao, John F Hartwig
Aug 25, 2005·Journal of the American Chemical Society·Pinjing ZhaoJohn F Hartwig

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Citations

Mar 30, 2010·Journal of the American Chemical Society·Tobias Seiser, Nicolai Cramer
Aug 31, 2011·Journal of the American Chemical Society·Hu LiZhang-Jie Shi
Oct 10, 2012·Journal of the American Chemical Society·Naoki IshidaMasahiro Murakami
Dec 18, 2013·Journal of the American Chemical Society·Lina DingKeiji Morokuma
Mar 26, 2009·Journal of the American Chemical Society·Jenni GoodmanD Christopher Roe
Sep 4, 2013·The Journal of Organic Chemistry·Yan ZhuJincheng Mao
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Jul 23, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Liqin XueZhenyang Lin
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Jan 5, 2016·Organic Letters·Chunliang ZhaoWei He
Dec 23, 2014·Chemical Communications : Chem Comm·Naoki IshidaMasahiro Murakami
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Mar 13, 2014·Chemistry : a European Journal·Haizhu YuZhi-Min Dang
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May 28, 2020·Chemical Communications : Chem Comm·Mingyang LiuBuxing Han
Jul 28, 2011·Angewandte Chemie·Tobias SeiserNicolai Cramer
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Apr 14, 2018·Journal of the American Chemical Society·Ying XiaGuangbin Dong
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