Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study

M J Maclean; Scott Walker; Tianfang Wang; P C H Eichinger; P J Sherman; J H Bowie

doi:10.1039/B916477D

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Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study

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Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study

M J Maclean, Scott Walker, Tianfang Wang, P C H Eichinger, P J Sherman and J H Bowie

Organic & Biomolecular Chemistry, Vol.8(2), pp.371-377

2010

DOI: https://doi.org/10.1039/B916477D

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Abstract

Selected carbanions react with carbon disulfide in a modified LCQ ion trap mass spectrometer to form adducts, which when collisionally activated, decompose by processes which in some cases identify the structures of the original carbanions. For example (i) C6H5- + CS2â†’ C6H5CS2-â†’ C6H5S- + CS, occurs through a 3-membered ring ipso transition state, and (ii) the reaction between C6H5CH2- and CS2 gives an adduct which loses H2S, whereas the adduct(s) formed between o-CH3C6H5- and CS2 loses H2S and CS. Finally, it is shown that decarboxylation of C6H5CH2CH2CO2- produces the β-phenylethyl anion (PhCH2CH2-), and that this thermalized anion reacts with CS2 to form C6H5CH2CH2CS2- which when energized fragments specifically by the process C6H5CH2CH2CS2-â†’ C6H5CH2-CHC(S)SH â†’ [(C6H5CH2CHCS) -SH] â†’ C6H5CH2CCS- + H2S. Experimental findings of processes (ii) and (iii) were aided by deuterium labelling studies, and all reaction profiles were studied by theoretical calculations at the UCCSD(T)/6-31+G(d,p)//B3LYP/6-31+G(d,p) level of theory unless indicated to the contrary.

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Title: Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study
Authors: M J Maclean (Author) - University of Adelaide
Scott Walker (Author) - University of Adelaide
Tianfang Wang (Author) - University of Adelaide
P C H Eichinger (Author) - University of Adelaide
P J Sherman (Author) - University of Adelaide
J H Bowie (Author) - University of Adelaide
Publication details: Organic & Biomolecular Chemistry, Vol.8(2), pp.371-377
Publisher: Royal Society of Chemistry (R S C) Publications
Date published: 2010
DOI: 10.1039/B916477D
ISSN: 1477-0520
Organisation Unit: School of Science and Engineering - Legacy; University of the Sunshine Coast, Queensland; School of Science, Technology and Engineering; Centre for Bioinnovation
Language: English
Record Identifier: 99450114502621
Output Type: Journal article

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