Please use this identifier to cite or link to this item:
|Title:||Fragmentation pathways of [Re2(μ-OR)3(CO)6]- (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry|
Andy Hor, T.S.
Van Kai, Y.
|Source:||Jiang, C., Andy Hor, T.S., Van Kai, Y., Henderson, W., McCaffrey, L.J. (2000). Fragmentation pathways of [Re2(μ-OR)3(CO)6]- (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry. Journal of the Chemical Society, Dalton Transactions (18) : 3197-3203. ScholarBank@NUS Repository. https://doi.org/10.1039/b003893h|
|Abstract:||The rhenium hydroxy and methoxy carbonyl complexes [Re2(u-OR)3(CO)6] (R = H or Me) have been studied by negative-ion electrospray mass spectrometry (ESMS). The complexes undergo facile exchange reactions with protic compounds, including alcohols and phenols. With dimethyl malonate, ester hydrolysis occurs giving carboxylatecontaining complexes, and with H2O2 or Bu'OOH, oxidation to ReO4 - occurs. The feasibility and extent of these reactions can conveniently, rapidly, and unambiguously be determined by electrospray mass spectrometry, and is dependent on the acidity and steric bulk of the protic compound. The results also suggest that the complexes can be used as versatile starting materials for the synthesis of a wide range of analogous [Re2(μ-OR)3(CO)6]- complexes by simple reaction with an excess of the appropriate alcohol. By varying the applied cone voltage the fragmentation pathways have been investigated; the hydroxy complex undergoes dehydration followed by CO loss, whereas for the methoxy complex -hydride elimination (and CO loss) is observed, with confirmation provided by deuterium labelling studies. Under ESMS conditions, the neutral complexes [Re2(μ-OR)2(μ-dppf)(CO)6] [R = H or Me; dppf= 1,1'-bis(diphenylphosphino)ferrocene] undergo substantial solvolysis and hydrolysis to give mainly mononuclear species; simple parent ions (e.g. [M + H]+) are not formed in appreciable abundance, probably due to the lack of an efficient ionisation pathway. ©The Royal Society of Chemistry 2000.|
|Source Title:||Journal of the Chemical Society, Dalton Transactions|
|Appears in Collections:||Staff Publications|
Show full item record
Files in This Item:
There are no files associated with this item.
checked on Feb 21, 2018
WEB OF SCIENCETM
checked on Jan 16, 2018
checked on Feb 18, 2018
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.