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Title: Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB/sub 4/H/sub 6/C - units. Crown carboranes

Abstract

The open-chain dialkynes EtC/identical to/C(CH/sub 2/)/sub n/C/identical to/CEt (n = 4, 6), the trialkyne HC/identical to/C(CH/sub 2/)/sub 5/C/identical to/CH, and the cyclic dialkynes CH/sub 2/(CH/sub 2/)/sub 4/C/identical to/C(CH/sub 2/)/sub n/C/identical to/C (n = 4-6) were treated with B/sub 5/H/sub 9/ and (C/sub 2/H/sub 5/)/sub 3/ to give the corresponding nido-carborane oligomers, in which the original -C/identical to/C- units are converted to -CB/sub 4/H/sub 6/C- nido-carborane cages. In each case, all available -C/identical to/C- groups were transformed to carborane moieties. No partially converted products (having both carborane and -C/identical to/C- groups in the chain) were found; when the B/sub 5/H/sub 9//-C/identical to/C- ratio employed was < 1, only completely converted products and unreacted starting materials were recovered at the end of the reaction. The open-chain carborane oligomers are viscous air-sensitive liquids that under undergo bridge deprotonation on treatment with NaH in THF solution; with excess NaH, one proton per carborane unit is removed. The resulting ionic species undergo complexation with Fe/sup 2+/ and oxidative fusion, forming products incorporating C/sub 4/B/sub 8/ cages. The cyclic bis(carborane) CH/sub 2/(CH/sub 2/)/sub 4/CB/sub 4/H/sub 6/C(CH/sub 2/)/sub 5/CB/sub 4/H/sub 6/C is an air-stable oil that can be deprotonated but does not under metal-promoted oxidative fusion. Allmore » products were characterized by /sup 11/B and /sup 1/H NMR, infrared, visible-uv, and mass spectroscopy, and the /sup 13/C NMR spectra of linear bis(carboranes) are reported. 9 references, 7 figures, 4 tables.« less

Authors:
;
Publication Date:
Research Org.:
Univ. of Virginia, Charlottesville (USA)
OSTI Identifier:
5853012
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 27:18
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKYNES; SYNTHESIS; CARBORANES; HETEROCYCLIC COMPOUNDS; BORON 11; CARBON 13; EXPERIMENTAL DATA; MASS SPECTROSCOPY; MOLECULAR STRUCTURE; NMR SPECTRA; PROTONS; ULTRAVIOLET SPECTRA; VISIBLE SPECTRA; BARYONS; BORON COMPOUNDS; BORON ISOTOPES; CARBON COMPOUNDS; CARBON ISOTOPES; DATA; ELEMENTARY PARTICLES; EVEN-ODD NUCLEI; FERMIONS; HADRONS; HYDROCARBONS; INFORMATION; ISOTOPES; LIGHT NUCLEI; NUCLEI; NUCLEONS; NUMERICAL DATA; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; SPECTRA; SPECTROSCOPY; STABLE ISOTOPES; 400201* - Chemical & Physicochemical Properties; 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation

Citation Formats

Boyter, Jr, H A, and Grimes, R N. Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB/sub 4/H/sub 6/C - units. Crown carboranes. United States: N. p., 1988. Web. doi:10.1021/ic00291a008.
Boyter, Jr, H A, & Grimes, R N. Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB/sub 4/H/sub 6/C - units. Crown carboranes. United States. doi:10.1021/ic00291a008.
Boyter, Jr, H A, and Grimes, R N. Wed . "Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB/sub 4/H/sub 6/C - units. Crown carboranes". United States. doi:10.1021/ic00291a008.
@article{osti_5853012,
title = {Nido-Carborane building-block reagents. 3. Cyclic and open-chain oligomers incorporating -CB/sub 4/H/sub 6/C - units. Crown carboranes},
author = {Boyter, Jr, H A and Grimes, R N},
abstractNote = {The open-chain dialkynes EtC/identical to/C(CH/sub 2/)/sub n/C/identical to/CEt (n = 4, 6), the trialkyne HC/identical to/C(CH/sub 2/)/sub 5/C/identical to/CH, and the cyclic dialkynes CH/sub 2/(CH/sub 2/)/sub 4/C/identical to/C(CH/sub 2/)/sub n/C/identical to/C (n = 4-6) were treated with B/sub 5/H/sub 9/ and (C/sub 2/H/sub 5/)/sub 3/ to give the corresponding nido-carborane oligomers, in which the original -C/identical to/C- units are converted to -CB/sub 4/H/sub 6/C- nido-carborane cages. In each case, all available -C/identical to/C- groups were transformed to carborane moieties. No partially converted products (having both carborane and -C/identical to/C- groups in the chain) were found; when the B/sub 5/H/sub 9//-C/identical to/C- ratio employed was < 1, only completely converted products and unreacted starting materials were recovered at the end of the reaction. The open-chain carborane oligomers are viscous air-sensitive liquids that under undergo bridge deprotonation on treatment with NaH in THF solution; with excess NaH, one proton per carborane unit is removed. The resulting ionic species undergo complexation with Fe/sup 2+/ and oxidative fusion, forming products incorporating C/sub 4/B/sub 8/ cages. The cyclic bis(carborane) CH/sub 2/(CH/sub 2/)/sub 4/CB/sub 4/H/sub 6/C(CH/sub 2/)/sub 5/CB/sub 4/H/sub 6/C is an air-stable oil that can be deprotonated but does not under metal-promoted oxidative fusion. All products were characterized by /sup 11/B and /sup 1/H NMR, infrared, visible-uv, and mass spectroscopy, and the /sup 13/C NMR spectra of linear bis(carboranes) are reported. 9 references, 7 figures, 4 tables.},
doi = {10.1021/ic00291a008},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 27:18,
place = {United States},
year = {1988},
month = {9}
}