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Title: Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway

Abstract

Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of typical divalent metals (Ca, Mn, Fe, Co, Ni, Zn, and Cu), comparing the results of collision-induced dissociation with the predictions from density functional theory. As for other solvated dications, dissociation channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, as one would expect from previous work on DMSO and acetonitrile complexes. Of primary interest is the highly unintuitive neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca, Mn, and Fe. We focus on understanding that process in the context of competing dissociation channels, as a function of metal identitymore » and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving a rearrangement of two acetone ligands and multiple transition states.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
909474
Report Number(s):
PNNL-SA-53468
KP1102010; TRN: US0703892
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A, 111(22):4748-4758; Journal Volume: 111; Journal Issue: 22
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; ACETONE; ACETONITRILE; CATIONS; CHEMISTRY; DISSOCIATION; ELECTRON TRANSFER; ETHYLENE; EVAPORATION; EXPLORATION; FRAGMENTATION; FUNCTIONALS; IONIZATION; MASS SPECTROSCOPY; PROTONS; SOLVATION; STABILITY

Citation Formats

Wu, Jianhua, Liu, Dan, Zhou, Jian-Ge, Hagelberg, Frank, Park, Sung S., and Shvartsburg, Alexandre A. Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway. United States: N. p., 2007. Web. doi:10.1021/jp068574z.
Wu, Jianhua, Liu, Dan, Zhou, Jian-Ge, Hagelberg, Frank, Park, Sung S., & Shvartsburg, Alexandre A. Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway. United States. doi:10.1021/jp068574z.
Wu, Jianhua, Liu, Dan, Zhou, Jian-Ge, Hagelberg, Frank, Park, Sung S., and Shvartsburg, Alexandre A. Wed . "Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway". United States. doi:10.1021/jp068574z.
@article{osti_909474,
title = {Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway},
author = {Wu, Jianhua and Liu, Dan and Zhou, Jian-Ge and Hagelberg, Frank and Park, Sung S. and Shvartsburg, Alexandre A.},
abstractNote = {Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of typical divalent metals (Ca, Mn, Fe, Co, Ni, Zn, and Cu), comparing the results of collision-induced dissociation with the predictions from density functional theory. As for other solvated dications, dissociation channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, as one would expect from previous work on DMSO and acetonitrile complexes. Of primary interest is the highly unintuitive neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca, Mn, and Fe. We focus on understanding that process in the context of competing dissociation channels, as a function of metal identity and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving a rearrangement of two acetone ligands and multiple transition states.},
doi = {10.1021/jp068574z},
journal = {Journal of Physical Chemistry A, 111(22):4748-4758},
number = 22,
volume = 111,
place = {United States},
year = {Wed May 16 00:00:00 EDT 2007},
month = {Wed May 16 00:00:00 EDT 2007}
}