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1. α-cymantrenylcarbenium ions

Author

Z. N. Parnes, Nikolay M. Loim, Pavel V. Petrovskii, V.I. Robas, and D. N. Kursanov

Subjects
Inorganic Chemistry, Chemistry, Computational chemistry, Carbon-13 NMR satellite, Organic Chemistry, Materials Chemistry, Physical and Theoretical Chemistry, Carbon-13 NMR, Biochemistry, Spectral line, Ion
Abstract

13C NMR spectra of some α-cymantrenylcarbenium ions and corresponding carbinols are reported. The data obtained are compared with the characteristics of the 13C NMR spectra of ferrocenyl-, phenyl- and cyclopropyl-carbenium ions. The mechanism of the carbenium centre stabilization by the adjacent metallocenyl radical is discussed.

Published
1976
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2. Interaction of lithium alkylamides or lithium dialkylamides with tetraphenylphosphonium chloride reaction course as a function of reaction conditions and dialkylamide structures

Author

P.V. Petrovsky, Nik A. Nesmeyanov, V.I. Robas, V. V. Mikul'shina, O. A. Reutov, and O. A. Rebrova

Subjects
Tetraphenylphosphonium chloride, Lithium amide, Ligand, Phosphorus, Organic Chemistry, Inorganic chemistry, chemistry.chemical_element, Charge-transfer complex, Biochemistry, Medicinal chemistry, Decomposition, Homolysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Materials Chemistry, Lithium, Physical and Theoretical Chemistry
Abstract

Reaction of Ph4P+Cl− with LiNHR (where R = CH3, C2H5, i-C3H7, n-C4H9, but not C(CH3)3) gives phosphineimines III, whereas the reaction with LiNR2 proceeds via three routes depending on the size of R and the dialkylamide excess. With larger R groups, homolytic decomposition of pentacoordinate phosphorus compounds occurs. With smaller R groups, Ph3P and PhNR2 are formed. Higher excesses of lithium amide result, probably, in ligand exchange at the pentacoordinate phosphorus followed by decomposition of the exchange products. Charge transfer complex intermediates are assumed to be formed in all the reactions.

Published
1976
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