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Matrix infrared spectroscopic and density functional theoretical investigations on thorium and uranium atom reactions with dimethyl ether.

Authors
  • Gong, Yu
  • Andrews, Lester
Type
Published Article
Journal
Dalton Transactions
Publisher
The Royal Society of Chemistry
Publication Date
Nov 14, 2011
Volume
40
Issue
42
Pages
11106–11114
Identifiers
DOI: 10.1039/c1dt10725a
PMID: 21769368
Source
Medline
License
Unknown

Abstract

Reactions of laser-ablated thorium and uranium atoms with dimethyl ether were investigated using matrix isolation infrared spectroscopy. Four types of reaction products for both uranium and thorium were identified using deuterium substituted samples as well as density functional frequency and energy calculations. Ground state uranium and thorium atoms react with dimethyl ether spontaneously to give the M(CH(3)OCH(3)) complexes (M = Th, U) on annealing, which are predicted to have C(2v) symmetry with triplet (Th) and quintet (U) ground states. Subsequent visible irradiation produces the divalent CH(3)OThCH(3) and CH(3)OUCH(3) insertion products with singlet and quintet states lowest in energy. Further UV irradiation induces isomerization of the CH(3)OMCH(3) molecules to the (CH(3))(2)MO isomers with M=O double bonds and pyramidal structures. In the presence of another dimethyl ether reagent, evidence for (CH(3)O)(2)M(CH(3))(2) molecules is also produced upon UV irradiation.

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