Please use this identifier to cite or link to this item: https://doi.org/10.1039/b003893h
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
Authors: Jiang, C.
Andy Hor, T.S. 
Van Kai, Y.
Henderson, W.
McCaffrey, L.J.
Issue Date: 2000
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
URI: http://scholarbank.nus.edu.sg/handle/10635/93856
ISSN: 1470479X
DOI: 10.1039/b003893h
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

18
checked on Feb 21, 2018

WEB OF SCIENCETM
Citations

17
checked on Jan 16, 2018

Page view(s)

13
checked on Feb 18, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.