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Gas‐phase chemistry of metal carbonyl anions: Reactions of Fe(CO) 2 − with methanol and its 13 C‐, D‐ and 18 O‐labelled analogues studied by fourier‐transform ion cyclotron resonance mass spectrometry
Author(s) -
van den Berg K. J.,
Ingemann S.,
Nibbering N. M. M.,
Gregor I. K.
Publication year - 1993
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1290070817
Subject(s) - chemistry , fourier transform ion cyclotron resonance , isotopomers , decarbonylation , methanol , deuterium , dehydrogenation , molecule , mass spectrometry , medicinal chemistry , ion , metal carbonyl , ion cyclotron resonance , metal , inorganic chemistry , analytical chemistry (journal) , organic chemistry , catalysis , cyclotron , physics , chromatography , quantum mechanics
The reactions of the metal dicarbonyl anion Fe(CO) 2 −with methanol and five of its isotopomers, namely CD 3 OH, CH 3 OD, CD 3 OH and CH 3 18 OH have been studied by the use of Fourier‐transform ion cyclotron resonance mass spectrometry. Three competitive reaction channels have been identified in these trapped‐ion/molecule studies which, for methanol, lead to the formation of three primary reaction products, namely [HFe(CO)(OCH) 3 ] − formed in a decarbonylation channel; Fe(CO) 3 −in a channel involving CH and OH bond activations and bis ‐dehydrogenation of a collision complex; and also [(CH 2 O)Fe(CO) 2 ] − in a separate channel involving the elimination of a single H 2 molecule. The primary product ion [HFe(CO)(OCH) 3 ] − further reacts with methanol to give a bis ‐alkoxy substituted metal carbonyl ion [(CH 3 O) 2 Fe(CO)] − at trapping times of several seconds. Complex deuterium isotope effects of an interactive nature with respect to the three reaction channels also have been observed.