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https://hdl.handle.net/2440/61719
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Type: | Journal article |
Title: | Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study |
Author: | Maclean, M. Walker, S. Wang, T. Eichinger, P. Sherman, P. Bowie, J. |
Citation: | Organic and Biomolecular Chemistry, 2010; 8(2):371-377 |
Publisher: | Royal Soc Chemistry |
Issue Date: | 2010 |
ISSN: | 1477-0520 1477-0539 |
Statement of Responsibility: | Micheal J. Maclean, Scott Walker, Tianfang Wang, Peter C. H. Eichinger, Patrick J. Sherman and John H. Bowie |
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) C(6)H(5)(-) + CS(2)--> C(6)H(5)CS(2)(-)--> C(6)H(5)S(-) + CS, occurs through a 3-membered ring ipso transition state, and (ii) the reaction between C(6)H(5)CH(2)(-) and CS(2) gives an adduct which loses H(2)S, whereas the adduct(s) formed between o-CH(3)C(6)H(5)(-) and CS(2) loses H(2)S and CS. Finally, it is shown that decarboxylation of C(6)H(5)CH(2)CH(2)CO(2)(-) produces the beta-phenylethyl anion (PhCH(2)CH(2)(-)), and that this thermalized anion reacts with CS(2) to form C(6)H(5)CH(2)CH(2)CS(2)(-) which when energized fragments specifically by the process C(6)H(5)CH(2)CH(2)CS(2)(-)--> C(6)H(5)CH(2)(-)CHC(S)SH --> [(C(6)H(5)CH(2)CH[double bond, length as m-dash]C[double bond, length as m-dash]S) (-)SH] --> C(6)H(5)CH(2)CCS(-) + H(2)S. 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. |
Rights: | © Royal Society of Chemistry 2010 |
DOI: | 10.1039/b916477d |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1039/b916477d |
Appears in Collections: | Aurora harvest Chemistry publications |
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