ESIMS studies and calculations on alkali-metal adduct ions of ruthenium olefin metathesis catalysts and their catalytic activity in metathesis reactions.
Electrospray ionization mass spectrometry (ESIMS) and subsequent tandem mass spectrometry (MS/MS) analyses were used to study some important metathesis reactions with the first-generation ruthenium catalyst 1, focusing on the ruthenium complex intermediates in the catalytic cycle. In situ cationization with alkali cations (Li(+), Na(+), K(+), and Cs(+)) using a microreactor coupled directly to the ESI ion source allowed mass spectrometric detection and characterization of the ruthenium species present in solution and particularly the catalytically active monophosphine-ruthenium intermediates present in equilibrium with the respective bisphosphine-ruthenium species in solution. Moreover, the intrinsic catalytic activity of the cationized monophosphine-ruthenium complex 1 aK(+) was directly demonstrated by gas-phase reactions with 1-butene or ethene to give the propylidene Ru species 3 aK(+) and the methylidene Ru species 4 aK(+), respectively. Ring-closing metathesis (RCM) reactions of 1,6-heptadiene (5), 1,7-octadiene (6) and 1,8-nonadiene (7) were studied in the presence of KCl and the ruthenium alkylidene intermediates 8, 9, and 10, respectively, were detected as cationized monophosphine and bisphosphine ruthenium complexes. Acyclic diene metathesis (ADMET) polymerization of 1,9-decadiene (14) and ring-opening metathesis polymerization (ROMP) of cyclooctene (18) were studied analogously, and the expected ruthenium alkylidene intermediates were directly intercepted from reaction solution and characterized unambiguously by their isotopic patterns and ESIMS/MS. ADMET polymerization was not observed for 1,5-hexadiene (22), but the formation of the intramolecularly stabilized monophosphine ruthenium complex 23 a was seen. The ratio of the signal intensities of the respective with potassium cationized monophosphine and bisphosphine alkylidene Ru species varied from [I(4a)]/[I(4)]=0.02 to [I(23a)]/[I(23)]=10.2 and proved to be a sensitive and quantitative probe for intramolecular pi-complex formation of the monophosphine-ruthenium species and of double bonds in the alkylidene chain. MS/MS spectra revealed the intrinsic metathesis catalytic activity of the potassium adduct ions of the ruthenium alkylidene intermediates 8 a, 9 a, 10 a, 15 a, and 19 a, but not 23 a by elimination of the respective cycloalkene in the second step of RCM. Computations were performed to provide information about the structures of the alkali metal adduct ions of catalyst 1 and the influence of the alkali metal ions on the energy profile in the catalytic cycle of the metathesis reaction.
Wang
Hao-Yang
HY
Institute of Pure and Applied Chemistry, University of Oldenburg, Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg, Germany.
Yim
Wai-Leung
WL
Klüner
Thorsten
T
Metzger
Jürgen O
JO