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Monocarbaborane anion chemistry. {COOH}, {CH2OH} and {CHO} units as functional groups on ten-vertex monocarbaborane anionic compounds

Lookup NU author(s): Emeritus Professor Bill Clegg

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Abstract

B10H14 reacts with para-C6H 4(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB 9H11-6-(C6H4-para-COOH)] - anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB9H9-2-(C6H 4-para-COOH)]- anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB9H9-1-(C6H 4-para-COOH)]- anion 3. Similarly, B10H 14 with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB9H13-6-(COOH)]- anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB9H9-2-(COOH)]- anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB9H 9-1-(COOH)]- anion 6. Reduction of the {COOH} anions 3 and 6 with diisobutylaluminium hydride gives the {CH2OH} hydroxy anions [closo-1-CB9H9-1-(C6H4-para-CH 2OH)]- 7 and [closo-1-CB9H9-1- (CH2OH)]- 8 respectively. The [closo-1-CB 9H9-1-(C6H4-para-CH 2OH)]- anion 7 can also be made via isomerisation of the [closo-2-CB9H9-2-(C6H4-para-CH 2OH)]- anion 9, in turn obtained from the [nido-6-CB 9H11-6-(C6H4-para-CH 2OH)]- anion 10, which is obtained from the reaction of B10H14 with terephthal-dicarboxaldehyde, C 6H4-para-(CHO)2, in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB9H9-1-(C6H 4-para-CHO)]- anion 11 and the aldehydic [closo-1-CB 9H9-1-(CHO)]- anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB9H9-1-C6H4-para-CH=N- NHC6H3(NO2)2]- anion 13 and the [closo-1-CB9H9-1-CH=N-NHC6H 3(NO2)2]- anion 14 respectively.


Publication metadata

Author(s): Franken A, Carr MJ, Clegg W, Kilner CA, Kennedy JD

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2004

Issue: 21

Pages: 3552-3561

Date deposited: 09/07/2010

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b411274a

DOI: 10.1039/b411274a


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