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https://hdl.handle.net/2440/61149
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Type: | Journal article |
Title: | Are the anions MeO(CO)n- (n=1 and 2) methoxide anion donors in the gas phase? A theoretical investigation |
Author: | Wang, T. Eichinger, P. Dua, S. Bowie, J. |
Citation: | Rapid Communications in Mass Spectrometry, 2010; 24(13):1895-1901 |
Publisher: | John Wiley & Sons Ltd |
Issue Date: | 2010 |
ISSN: | 0951-4198 1097-0231 |
Statement of Responsibility: | Tianfang Wang, Peter C. H. Eichinger, Suresh Dua and John H. Bowie |
Abstract: | 1. The anions CH(3)O-(-)CO and CH(3)OCO-(-)CO are both methoxide anion donors. The processes CH(3)O-(-)CO --> CH(3)O(-) + CO and CH(3)OCO-CO --> CH(3)O(-) + 2CO have DeltaG values of +8 and -68 kJ mol(-1), respectively, at the CCSD(T)/6-311++G(2d, 2p)//B3LYP/6-311++G(2d,2p) level of theory. 2. The reactions CH(3)OCOCO(2) (-) --> CH(3)OCO(2) (-) + CO (DeltaG = -22 kJ mol(-1)) and CH(3)COCH(O(-))CO(2)CH(3) --> CH(3)COCH(O(-))OCH(3) + CO (DeltaG = +19 kJ mol(-1)) proceed directly from the precursor anions via the transition states (CH(3)OCO...CO(2))(-) and (CH(3)COCHO...CH(3)OCO)(-), respectively. 3. Anion CH(3)COCH(O(-))CO(2)CH(3) undergoes methoxide anion transfer and loss of two molecules of CO in the reaction sequence CH(3)COCH(O(-))CO(2)CH(3) --> CH(3)CH(O(-))COCO(2)CH(3) --> [CH(3)CHO (CH(3)OCO-(-)CO)] --> CH(3)CH(O(-))OCH(3) + 2CO (DeltaG = +9 kJ mol(-1)). The hydride ion transfer in the first step is a key feature of the reaction sequence. |
Rights: | © 2010 John Wiley & Sons |
DOI: | 10.1002/rcm.4586 |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1002/rcm.4586 |
Appears in Collections: | Aurora harvest Chemistry and Physics publications |
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