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Title: Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)/sub 2/C/sub 2/B/sub 4/H/sub 6/ derivatives and (C/sub 6/H/sub 5/)/sub 2/C/sub 2/B/sub 4/H/sub 6/: synthesis and properties

Abstract

The preparation and chemistry of nido-2,3-R/sub 2/C/sub 2/C/sub 2/B/sub 4/H/sub 6/ carboranes in which R is n-butyl, isopentyl, n-hexyl, and phenyl was investigated in order to further assess the steric and electronic influence of the R groups on the properties of the nido-C/sub 2/B/sub 4/ cage, especially with respect to metal complexation at the C/sub 2/B/sub 3/ face and metal-promoted oxidative fusion. The three dialkyl derivatives were prepared from the corresponding dialkylacetylenes via reaction with B/sub 5/H/sub 9/ and triethylamine, but the diphenyl compound could not be prepared in this manner and was obtained instead in a thermal reaction of B/sub 5/H/sub 9/ with diphenylacetylene in the absence of amine. All four carboranes are readily bridge-deprotonated by NaH in THF, and the anions of the dialkyl species, on treatment with FeCl/sub 2/ and air oxidation, generate the respective R/sub 4/C/sub 4/B/sub 8/H/sub 8/ carborane fusion products were R = n-C/sub 4/H/sub 9/, i-C/sub 5/H/sub 11/ or n-C/sub 6/H/sub 13/. The diphenylcarborane anion Ph/sub 2/C/sub 2/B/sub 4/H/sub 5//sup /minus// did not form detectable metal complexes with Fe/sup 2+/, Co/sup 2+/, or Ni/sup 2+/, and no evidence of a Ph/sub 4/C/sub 4/B/sub 8/H/sub 8/ fusion product has been found. Treatment of Ph/submore » 2/C/sub 2/B/sub 4/H/sub 6/ with Cr(CO)/sub 6/ did not lead to metal coordination of the phenyl rings, unlike (PhCH/sub 2/)/sub 2/C/sub 2/B/sub 4/H/sub 6/, which had previously been shown to form mono- and bis(tricarbonylchromium) complexes. However, the reaction of Ph/sub 2/C/sub 2/B/sub 4/H/sub 5//sup /minus//, CoCl/sub 2/, and (PhPCH/sub 2/)/sub 2/ did give 1,1-(Ph/sub 2/PCH/sub 2/)/sub 2/-1-Cl-1,2,3-Co(Ph/sub 2/C/sub 2/B/sub 4/H/sub 4/), the only case in which metal complexation of the diphenylcarborane was observed. 14 references, 3 figures, 3 tables.« less

Authors:
;
Publication Date:
Research Org.:
Univ. of Virginia, Charlottesville (USA)
OSTI Identifier:
5762150
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; CARBORANES; SYNTHESIS; HETEROCYCLIC COMPOUNDS; BORON 11; EXPERIMENTAL DATA; MOLECULAR STRUCTURE; NMR SPECTRA; ULTRAVIOLET SPECTRA; BORON COMPOUNDS; BORON ISOTOPES; CARBON COMPOUNDS; DATA; INFORMATION; ISOTOPES; LIGHT NUCLEI; NUCLEI; NUMERICAL DATA; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; SPECTRA; 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. 2. Bulky-substituent (alkyl)/sub 2/C/sub 2/B/sub 4/H/sub 6/ derivatives and (C/sub 6/H/sub 5/)/sub 2/C/sub 2/B/sub 4/H/sub 6/: synthesis and properties. United States: N. p., 1988. Web. doi:10.1021/ic00291a007.
Boyter, Jr, H A, & Grimes, R N. Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)/sub 2/C/sub 2/B/sub 4/H/sub 6/ derivatives and (C/sub 6/H/sub 5/)/sub 2/C/sub 2/B/sub 4/H/sub 6/: synthesis and properties. United States. doi:10.1021/ic00291a007.
Boyter, Jr, H A, and Grimes, R N. Wed . "Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)/sub 2/C/sub 2/B/sub 4/H/sub 6/ derivatives and (C/sub 6/H/sub 5/)/sub 2/C/sub 2/B/sub 4/H/sub 6/: synthesis and properties". United States. doi:10.1021/ic00291a007.
@article{osti_5762150,
title = {Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)/sub 2/C/sub 2/B/sub 4/H/sub 6/ derivatives and (C/sub 6/H/sub 5/)/sub 2/C/sub 2/B/sub 4/H/sub 6/: synthesis and properties},
author = {Boyter, Jr, H A and Grimes, R N},
abstractNote = {The preparation and chemistry of nido-2,3-R/sub 2/C/sub 2/C/sub 2/B/sub 4/H/sub 6/ carboranes in which R is n-butyl, isopentyl, n-hexyl, and phenyl was investigated in order to further assess the steric and electronic influence of the R groups on the properties of the nido-C/sub 2/B/sub 4/ cage, especially with respect to metal complexation at the C/sub 2/B/sub 3/ face and metal-promoted oxidative fusion. The three dialkyl derivatives were prepared from the corresponding dialkylacetylenes via reaction with B/sub 5/H/sub 9/ and triethylamine, but the diphenyl compound could not be prepared in this manner and was obtained instead in a thermal reaction of B/sub 5/H/sub 9/ with diphenylacetylene in the absence of amine. All four carboranes are readily bridge-deprotonated by NaH in THF, and the anions of the dialkyl species, on treatment with FeCl/sub 2/ and air oxidation, generate the respective R/sub 4/C/sub 4/B/sub 8/H/sub 8/ carborane fusion products were R = n-C/sub 4/H/sub 9/, i-C/sub 5/H/sub 11/ or n-C/sub 6/H/sub 13/. The diphenylcarborane anion Ph/sub 2/C/sub 2/B/sub 4/H/sub 5//sup /minus// did not form detectable metal complexes with Fe/sup 2+/, Co/sup 2+/, or Ni/sup 2+/, and no evidence of a Ph/sub 4/C/sub 4/B/sub 8/H/sub 8/ fusion product has been found. Treatment of Ph/sub 2/C/sub 2/B/sub 4/H/sub 6/ with Cr(CO)/sub 6/ did not lead to metal coordination of the phenyl rings, unlike (PhCH/sub 2/)/sub 2/C/sub 2/B/sub 4/H/sub 6/, which had previously been shown to form mono- and bis(tricarbonylchromium) complexes. However, the reaction of Ph/sub 2/C/sub 2/B/sub 4/H/sub 5//sup /minus//, CoCl/sub 2/, and (PhPCH/sub 2/)/sub 2/ did give 1,1-(Ph/sub 2/PCH/sub 2/)/sub 2/-1-Cl-1,2,3-Co(Ph/sub 2/C/sub 2/B/sub 4/H/sub 4/), the only case in which metal complexation of the diphenylcarborane was observed. 14 references, 3 figures, 3 tables.},
doi = {10.1021/ic00291a007},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 27:18,
place = {United States},
year = {1988},
month = {9}
}