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Synthesis of Organouranium(IV) Triflates from U(OTf) 4 or from Alkyl or Amide Precursors
Author(s) -
Berthet Jean Claude,
Nierlich Martine,
Ephritikhine Michel
Publication year - 2002
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 - 10.1002/1099-0682(200203)2002:4<850::aid-ejic850>3.0.co;2-y
Subject(s) - chemistry , trifluoromethanesulfonate , pyridine , denticity , amide , medicinal chemistry , pyridinium , protonolysis , alkyl , cyclopentadienyl complex , tetrafluoroborate , crystal structure , adduct , stereochemistry , catalysis , organic chemistry , ionic liquid
The uranium(IV) triflate [U(OTf) 4 ] ( 1 ) (OTf = OSO 2 CF 3 ) gives stable adducts with Lewis bases, such as [U(OTf) 4 (py)] ( 2 ) (py = pyridine). The crystal structure of a solvate of [U(OTf) 4 (OPPh 3 ) 3 ] ( 3 ), which exhibits a bidentate OTf group, has been determined. Substitution of the triflate ligands of 1 with LiNEt 2 , Kacac (acac = MeCOCHCOMe), KCp (Cp = η‐C 5 H 5 ), and K 2 COT (COT = η‐C 8 H 8 ) has led to the formation of [U(NEt 2 ) 4 ], [U(acac) 4 ], [U(Cp) 3 (OTf)] ( 4 ), and [U(COT)(OTf) 2 (py)] ( 5 ), respectively. However, the bis(cyclopentadienyl) compounds [U(Cp*) 2 (OTf) 2 ] ( 6 ) (Cp* = η‐C 5 Me 5 ) and [U(Cp) 2 (OTf) 2 (py)] ( 7 ) could not be prepared from 1 . Complexes 4−7 have been isolated in good yields from the protonolysis reactions of the corresponding alkyl or amide precursors by means of pyridinium triflate. Compound 5 has also been prepared by treating [U(COT) 2 ] with either [pyH][OTf] or 1 in pyridine. The crystal structures of [U(Cp) 2 (OTf) 2 (py) 2 ] ( 8 ) and [U(COT)(OTf) 2 (OPPh 3 ) 2 ]·0.5py ( 9 ) have been determined.