A Modern Twist to a Classic Synthetic Route: Ph3Bi-Based Redox Transmetalation Protolysis (RTP) for the Preparation of Barium Metalorganic Species

Yuriko Takahashi, Anna O'Brien, Glen B. Deacon, Philip C. Andrews, Melanie Wolf, Ana Torvisco, Miriam M. Gillett-Kunnath, Karin Ruhlandt-Senge

Research output: Research - peer-reviewArticle

Abstract

This paper reports advances in redox transmetalation/protolysis (RTP) utilizing the readily available Ph3Bi for the synthesis of a series of barium metal-organic species. On the basis of easily available starting materials, an easy one-pot procedure, and workup, we have obtained BaL2 compounds (L = bis(trimethylsilyl)amide, phenyl(trimethylsilyl)amide, pentamethylcyclopentadienide, fluorenide, 2,6-di-isopropylphenolate, and 3,5-diphenylpyrazolate) quantitatively by sonication of an excess of barium metal with triphenylbismuth and HL in perdeuterotetrahydrofuran, as established by NMR measurements. Rates of conversion are affected by both pKa and bulk of HL. Competition occurs from direct reaction of Ba with HL, thereby enhancing the overall conversion, the effect being pronounced for the less bulky and more acidic ligands. Overall, the method significantly adds to the synthetic armory for barium metal-organic/organometallic compounds.

LanguageEnglish (US)
Pages11480-11489
Number of pages10
JournalInorganic Chemistry
Volume56
Issue number19
DOIs
StatePublished - Oct 2 2017

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barium
routes
preparation
metals
Barium
Metals
Oxidation-Reduction
amides
Amides
organometallic compounds
nuclear magnetic resonance
ligands
synthesis
Organometallic Compounds
Sonication
Nuclear magnetic resonance
Ligands
triphenyl bismuth

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

A Modern Twist to a Classic Synthetic Route : Ph3Bi-Based Redox Transmetalation Protolysis (RTP) for the Preparation of Barium Metalorganic Species. / Takahashi, Yuriko; O'Brien, Anna; Deacon, Glen B.; Andrews, Philip C.; Wolf, Melanie; Torvisco, Ana; Gillett-Kunnath, Miriam M.; Ruhlandt-Senge, Karin.

In: Inorganic Chemistry, Vol. 56, No. 19, 02.10.2017, p. 11480-11489.

Research output: Research - peer-reviewArticle

Takahashi, Yuriko ; O'Brien, Anna ; Deacon, Glen B. ; Andrews, Philip C. ; Wolf, Melanie ; Torvisco, Ana ; Gillett-Kunnath, Miriam M. ; Ruhlandt-Senge, Karin. / A Modern Twist to a Classic Synthetic Route : Ph3Bi-Based Redox Transmetalation Protolysis (RTP) for the Preparation of Barium Metalorganic Species. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 19. pp. 11480-11489
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