Premium
Bringing Redox Reactivity to a Redox Inactive Metal Center – E–I (E = C, Si) Bond Cleavage with a Thorium Bis(α‐diimine) Complex
Author(s) -
Mrutu Agnes,
Barnes Charles L.,
Bart Suzanne C.,
Walensky Justin R.
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300390
Subject(s) - chemistry , reactivity (psychology) , bond cleavage , redox , tetrahydrofuran , ligand (biochemistry) , diimine , acetonitrile , adduct , medicinal chemistry , transition metal , metal , stereochemistry , inorganic chemistry , catalysis , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology , solvent
As the reactivity of transition‐metal complexes with redox‐active ligands has gained significant attention in recent years, we have begun expanding to the actinides. Here, we report the synthesis, characterization, and reactivity of ( Mes DAB Me ) 2 Th(THF) { 1 , Mes DAB Me = [MesNC(Me)=C(Me)NMes] 2– , Mes = 2,4,6‐trimethylphenyl, THF = tetrahydrofuran}, which cleaves the C–I bond in CH 3 I with subsequent Th–I and C–C bond formation to produce ( Mes DAB Me )( Mes DAB Me 2)ThI { 2 , Mes DAB Me 2= [MesN=C(Me)C(Me) 2 NMes] – }. When 2 is crystallized in acetonitrile, the solvated adduct ( Mes DAB Me )( Mes DAB Me 2)ThI(NCCH 3 ) ( 2 ‐MeCN) is isolated. The reaction of 2 equiv. of 1 with Me 3 SiI produces ( Mes DAB Me ) 2 ThI ( 3 ) and Me 3 SiSiMe 3 . In 3 , one Mes DAB Me ligand is now monoanionic and provides an electron to cleave the Si–I bond. This represents a rare example of the reactivity of thorium with a redox‐active ligand.