Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry

Abstract

Supporting InformationTable of Contents 1.) Anion-mode ESI mass spectra of Li 0.8 Cu n,s Bu 0.8 ( 13 CN) solutions (Figures S1 -S4) S2 2.) Mass spectra of mass-selected Li 2 Cu 3 n,s Bu 2 (OH)( 13 CN) 3 − and Li 3 Cu 4 n,s Bu 3 (OH)( 13 CN) 4 − anions and their fragment ions (Figures S5 -S8) S4

Low‐Valent Ate Complexes Formed in Cobalt‐Catalyzed Cross‐Coupling Reactions with 1,3‐Dienes as Additives

“…Being highly electropositive, lithium and magnesium readily form cations, whereas more electronegative cobalt strongly prefers anionic ate complexes. Very similar behavior has previously been observed for the transmetalation of iron, copper, and zinc precursors as well.…”

“…The analyte ions passed through a glass capillary (capillary exit: ±20 V), a skimmer (±20 V), and two transfer octopoles (±4.0 V/±1.7 V) before entering the ion trap. Previous work has shown that these settings give rise to very mild conditions and preserve even labile organometallic ions . The helium‐filled ion trap was operated at a trap drive of 40 to ensure an efficient trapping of ions in the recorded m / z range of 50–1200.…”

Which cations form upon CSI or ESI of solutions of Grignard reagents?

“…A second series of experiments used a three-dimensional HCT quadrupole-ion trap (QIT) instrument (Bruker Daltonik). Like in previous studies, [10,11] mild ion-transfer conditions were applied to prevent unwanted decomposition reactions. The ion trap was operated at a trap drive of 40.…”

“…†, ‡ In previous investigations of reactive organometallics, we did not find any evidence for its persistence in the ion sources and its interference with the probed ions. [11,13,14] This comparison suggests that only the most reactive analyte ions react with the remaining traces of methanol sufficiently fast to cause an observable effect.…”

Copper‐catalyzed reactions: Research in the gas phase

“…However, the question of the aggregation state of cyanocuprates in solution still receives continuous attention. Putau and Koszinowski decided to address this question with the ESI-MS studies of cyanocuprates in THF (Putau & Koszinowski, 2010). To this end, solutions were prepared by addition of RLi to a suspension of CuCN in THF under argon atmosphere at À78˚C.…”