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 language | English (US) |
|---|---|
| Pages (from-to) | 6058-6063 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 110 |
| Issue number | 18 |
| DOIs | |
| State | Published - Jan 1 1988 |
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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, Louis M; Smith, B. D.; Williard, Paul G.
In: Journal of the American Chemical Society, Vol. 110, No. 18, 01.01.1988, p. 6058-6063.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Structures of Lithium Salts of 2, 3, 3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State
AU - Jackman, L. M.
AU - Scarmoutzos, Louis M
AU - Smith, B. D.
AU - Williard, Paul G.
PY - 1988/1/1
Y1 - 1988/1/1
N2 - 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.
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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U2 - 10.1021/ja00226a021
DO - 10.1021/ja00226a021
M3 - Article
VL - 110
SP - 6058
EP - 6063
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 18
ER -