Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Matthew C. Crowe, Ramesh N. Kapoor, Francisco Cervantes-Lee, L. Párkányí, Louis Schulte, Keith H. Pannell, Jennifer S. Brodbelt

Research output: Contribution to journalArticle

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Abstract

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H 4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4) 2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu) 2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.

Original languageEnglish
Pages (from-to)6415-6424
Number of pages10
JournalInorganic Chemistry
Volume44
Issue number18
DOIs
Publication statusPublished - Sep 5 2005

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Electrospray ionization
Rare earth elements
Oxides
Mass spectrometry
mass spectroscopy
rare earth elements
quadrupoles
Ions
Ligands
ionization
ligands
oxides
interactions
Lanthanoid Series Elements
Metals
Stoichiometry
Nitrates
nitrates
stoichiometry
phosphates

ASJC Scopus subject areas

  • Inorganic Chemistry

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Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-earth elements using electrospray ionization quadrupole ion trap mass spectrometry. / Crowe, Matthew C.; Kapoor, Ramesh N.; Cervantes-Lee, Francisco; Párkányí, L.; Schulte, Louis; Pannell, Keith H.; Brodbelt, Jennifer S.

In: Inorganic Chemistry, Vol. 44, No. 18, 05.09.2005, p. 6415-6424.

Research output: Contribution to journalArticle

Crowe, Matthew C. ; Kapoor, Ramesh N. ; Cervantes-Lee, Francisco ; Párkányí, L. ; Schulte, Louis ; Pannell, Keith H. ; Brodbelt, Jennifer S. / Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-earth elements using electrospray ionization quadrupole ion trap mass spectrometry. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 18. pp. 6415-6424.
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AB - Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H 4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4) 2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu) 2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.

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