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Double Reduction of 4,4′‐Bipyridine and Reductive Coupling of Pyridine by Two Thorium(III) Single‐Electron Transfers
Author(s) -
Formanuik Alasdair,
Ortu Fabrizio,
Liu Jingjing,
Nodaraki Lydia E.,
Tuna Floriana,
Kerridge Andrew,
Mills David P.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605974
Subject(s) - actinide , uranium , thorium , chemistry , reactivity (psychology) , pyridine , lanthanide , redox , inorganic chemistry , bipyridine , medicinal chemistry , crystallography , organic chemistry , crystal structure , physics , ion , nuclear physics , medicine , alternative medicine , pathology
The redox chemistry of uranium is burgeoning and uranium(III) complexes have been shown to promote many interesting synthetic transformations. However, their utility is limited by their reduction potentials, which are smaller than many non‐traditional lanthanide(II) complexes. Thorium(III) has a greater redox potential so it should present unprecedented opportunities for actinide reactivity but as with uranium(II) and thorium(II) chemistry, these have not yet been fully realized. Herein we present reactivity studies of two equivalents of [Th(Cp′′) 3 ] ( 1 , Cp′′={C 5 H 3 (SiMe 3 ) 2 ‐1,3}) with 4,4′‐bipyridine or two equivalents of pyridine to give [{Th(Cp′′) 3 } 2 {μ‐(NC 5 H 4 ) 2 }] ( 2 ) and [{Th(Cp′′) 3 } 2 {μ‐(NC 5 H 5 ) 2 }] ( 3 ), respectively. As relatively large reduction potentials are required to effect these transformations we have shown that thorium(III) can promote reactions that uranium(III) cannot, opening up promising new reductive chemistry for the actinides.