Structures of Lithium Salts of 2, 3, 3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State

L. M. Jackman, L. M. Scarmoutzos, B. D. Smith, Paul G. Williard

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

An X-ray crystal structure of lithium 2, 3, 3-trimethylindolenide etherate shows it to be a disolvated dimer having a η3-azaallyl-type structure. The structures of the salt in several solvents have been established by studies of 13C chemical shifts, 6Li, 15N spin-spin splitting, 7Li quadrupole splitting constants, and apparent degrees of aggregation determined by vapor pressure barometry. It is the η3-azaallyl dimer disolvate in diethyl ether, a tetrasolvated dimer in dioxolane, a mixture of monomer and tetrasolvated dimer in tetrahydrofuran, and a monomer in pyridine. The species are characterized by 7Li quadrupole splitting constants of 230, 156, 180–190 (0.27-0.75 M), and 217 kHz, respectively. In diethyl ether with 4 equiv of hexamethylphosphoric triamide, the salt is a mixture of monomeric and triple ion species. Lithium 5-methoxy-2, 3, 3-trimethylindolenide forms similar species except that, in tetrahydrofuran, the tendency for dimer formation is enhanced, which leads to a higher proportion of C- to N-methylation in its reaction with methyl chloride in that solvent.

Original languageEnglish (US)
Pages (from-to)6058-6063
Number of pages6
JournalJournal of the American Chemical Society
Volume110
Issue number18
DOIs
StatePublished - Aug 1988

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Lithium
Dimers
Ether
Salts
Hempa
Methyl Chloride
Derivatives
Vapor Pressure
Methylation
X-Rays
Ions
Ethers
Monomers
Chemical shift
Vapor pressure
Pyridine
Agglomeration
Crystal structure
tetrahydrofuran
X rays

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Structures of Lithium Salts of 2, 3, 3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State. / Jackman, L. M.; Scarmoutzos, L. M.; Smith, B. D.; Williard, Paul G.

In: Journal of the American Chemical Society, Vol. 110, No. 18, 08.1988, p. 6058-6063.

Research output: Contribution to journalArticle

Jackman, L. M. ; Scarmoutzos, L. M. ; Smith, B. D. ; Williard, Paul G. / Structures of Lithium Salts of 2, 3, 3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State. In: Journal of the American Chemical Society. 1988 ; Vol. 110, No. 18. pp. 6058-6063.
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abstract = "An X-ray crystal structure of lithium 2, 3, 3-trimethylindolenide etherate shows it to be a disolvated dimer having a η3-azaallyl-type structure. The structures of the salt in several solvents have been established by studies of 13C chemical shifts, 6Li, 15N spin-spin splitting, 7Li quadrupole splitting constants, and apparent degrees of aggregation determined by vapor pressure barometry. It is the η3-azaallyl dimer disolvate in diethyl ether, a tetrasolvated dimer in dioxolane, a mixture of monomer and tetrasolvated dimer in tetrahydrofuran, and a monomer in pyridine. The species are characterized by 7Li quadrupole splitting constants of 230, 156, 180–190 (0.27-0.75 M), and 217 kHz, respectively. In diethyl ether with 4 equiv of hexamethylphosphoric triamide, the salt is a mixture of monomeric and triple ion species. Lithium 5-methoxy-2, 3, 3-trimethylindolenide forms similar species except that, in tetrahydrofuran, the tendency for dimer formation is enhanced, which leads to a higher proportion of C- to N-methylation in its reaction with methyl chloride in that solvent.",
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AB - An X-ray crystal structure of lithium 2, 3, 3-trimethylindolenide etherate shows it to be a disolvated dimer having a η3-azaallyl-type structure. The structures of the salt in several solvents have been established by studies of 13C chemical shifts, 6Li, 15N spin-spin splitting, 7Li quadrupole splitting constants, and apparent degrees of aggregation determined by vapor pressure barometry. It is the η3-azaallyl dimer disolvate in diethyl ether, a tetrasolvated dimer in dioxolane, a mixture of monomer and tetrasolvated dimer in tetrahydrofuran, and a monomer in pyridine. The species are characterized by 7Li quadrupole splitting constants of 230, 156, 180–190 (0.27-0.75 M), and 217 kHz, respectively. In diethyl ether with 4 equiv of hexamethylphosphoric triamide, the salt is a mixture of monomeric and triple ion species. Lithium 5-methoxy-2, 3, 3-trimethylindolenide forms similar species except that, in tetrahydrofuran, the tendency for dimer formation is enhanced, which leads to a higher proportion of C- to N-methylation in its reaction with methyl chloride in that solvent.

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