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Nucleophilic Addition of Phosphate to Coordinated (Arene)manganes Tricarbonyl Cations

  • Chung, Young-Keun (Department of Chemistry, College of Natural Sciences, Seoul National University) ;
  • Bae, Hye-Kyung (Inorganic Chemistry Laboratory, Korea Advanced Institute of Science and Technology) ;
  • Jung, Il-Nam (Inorganic Chemistry Laboratory, Korea Advanced Institute of Science and Technology)
  • Published : 1988.12.20

Abstract

[(Benzene)Mn$(CO)_3$]$^+$ reacts with NaP(O) (OR)$_2$ (R = Me, Et, Ph) to give the phosphonate compound 1. Compound 1 reacts with R'Li (R = Me, Ph, $^nBu, ^tBu$) to yield the isomerized compound 2 and the alkylated compound 3. [(Toluene)Mn$(CO)_3$]$^+$ reacts with NaP(O)$(OMe)_2$ to give the phosphonate complexes 1-A and 1-B. Treatment of 1-A with $^tBuLi$ in THF affords complexes 3-A and 3-B with the later major. With 1-B only the complex 3-C is formed. [(Anisole)Mn$(CO)_3$]$^+$ reacts with NaP(O)$(OMe)_2$ to give the phosphate complex 1-C, which on treatment with $^tBuLi$ and then $H_2O$ yields compound 3-D. After demetallation of compound 3-D, meta-tertbutyl-anisole is obtained in a reasonable yield.

Keywords

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Cited by

  1. Addition of Stabilized Carbanions to Cationic (η6-Arene)tricarbonylmanganese Complexes: Syntheses of Homo (Mn-Mn) and Hetero (Mn-Cr) Dinuclear Complexes vol.1999, pp.3, 1988, https://doi.org/10.1002/(sici)1099-0682(199903)1999:3<421::aid-ejic421>3.0.co;2-0
  2. Reactivity of Metallophosphide Anions with Electrophilic (Arene)tricarbonylmetal Complexes vol.2003, pp.10, 1988, https://doi.org/10.1002/ejic.200200531