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Title: Electrospray production and collisional dissociation of lanthanide/methylsulfonyl anion complexes: Sulfur dioxide anion as a ligand

For this study, gas-phase lanthanide-SO 2 complexes, Ln(CH 3SO 2) 3(SO 2) -, were produced by collision induced dissociation (CID) of Ln(CH 3SO 2) 4 - precursors prepared by electrospray ionization. For all lanthanides except Eu, CID of Ln(CH 3SO 2) 4 - resulted in CH 3 loss to form Ln(CH 3SO 2) 3(SO 2) -, which spontaneously react with O 2 to form Ln(CH 3SO 2) 3(O 2) -. CID of Eu(CH 3SO 2) 4 - produced only Eu(CH 3SO 2) 3 -, with reduction from Eu(III) to Eu(II). For Ln = Yb and Sm, the Ln(CH 3SO 2) 4 - underwent neutral ligand loss to form Ln(CH 3SO 2) 3 -, which reacted with O 2 to yield Ln(CH 3SO 2) 3(O 2) -, recovering the Ln(III) oxidation state. The CID results show parallels to condensed-phase Ln 3+/Ln 2+ redox chemistry. Density functional theory (DFT) calculations on Ln(CH 3SO 2) 3(SO 2) - for Ln = La, Yb and Lu reveal that SO 2 acts as a bidentate oxygen bound ligand for doublet ground-state La(CH 3SO 2) 3(SO 2) - and Lu(CH 3SO 2) 3(SO 2) -, while the ground state for Yb(CH 3SO 2) 3(SO 2) -more » is an open-shell singlet with a monodentate SO 2 ligand. Loss of CH 3 is computed to be much more favorable than neutral ligand loss for La(CH 3SO 2) 4 - and Lu(CH 3SO 2) 4 -, whereas both channels are comparable in energy for Yb(CH 3SO 2) 4 -, in accord with the experiments. DFT results for fragmentation of Cu(CH 3SO 2) 2 - reveal that formation of the organometallic complex, Cu(CH 3SO 2)(CH 3) -, is energetically most favorable, in agreement with contrasting fragmentation pathways of copper and lanthanide complexes.« less
Authors:
 [1] ;  [2] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of Calabria, Arcavacata (Italy). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
International Journal of Mass Spectrometry
Additional Journal Information:
Journal Volume: 392; Journal Issue: C; Related Information: © 2015 Elsevier B.V. All rights reserved.; Journal ID: ISSN 1387-3806
Publisher:
Elsevier
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Collision induced dissociation; Lanthanide complexes; Methane sulfinate; Sulfur dioxide anion; Density functional theory; Divalent lanthanides
OSTI Identifier:
1461098
Alternate Identifier(s):
OSTI ID: 1347244