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Syntheses and Structures of Bis(aryloxo)fluoroytterbium(III) Complexes, [Yb(OAr) 2 F(THF)] 2 (OAr = OC 6 H 2 ‐2,6‐ t Bu 2 ‐4‐R; R = H, Me, t Bu), and Bis(cyclopentadienyl)fluoroytterbium(III) Complexes, [YbCp 2 F] 3 , [Yb(MeCp) 2 F] 4 , [YbCp 2 F(OPPh 3 )] 2 , and [Yb(MeCp) 2 F(THF)] 2
Author(s) -
Deacon Glen B.,
Meyer Gerd,
Stellfeldt Dirk
Publication year - 2000
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/(sici)1099-0682(200005)2000:5<1061::aid-ejic1061>3.0.co;2-7
Subject(s) - chemistry , cyclopentadienyl complex , ytterbium , crystallography , fluoride , medicinal chemistry , stereochemistry , ring (chemistry) , catalysis , inorganic chemistry , organic chemistry , physics , optoelectronics , doping
Reaction of [Yb(OAr) 2 (THF) 3 ] (OAr = OC 6 H 2 ‐2,6‐ t Bu 2 ‐4‐R; R = H, Me, t Bu) with perfluorodecalin in THF at room temperature results in C–F activation and formation of the first heteroleptic aryloxofluorolanthanoid complexes, [Yb(OAr) 2 F(THF)] 2 . Oxidation of bis(cyclopentadienyl)ytterbium(II) with perfluoro(methylcyclohexane) or perfluorodecalin in DME surprisingly gives unsolvated [YbCp 2 F] 3 . The analogous reaction of bis(methylcyclopentadienyl)ytterbium(II) yields unsolvated [Yb(MeCp) 2 F] 4 , whilst in THF, the oxidation provides [Yb(MeCp) 2 F(THF)] 2 . Treatment of [YbCp 2 F(THF)] 2 with triphenylphosphane oxide gives [YbCp 2 F(OPPh 3 )] 2 . X‐ray structure determinations revealed [Yb(OAr) 2 F(THF)] 2 (R = H or t Bu) to be centrosymmetric fluoride‐bridged dimers with five‐coordination for ytterbium. Examination of the structures of the cyclopentadienyl complexes showed that [YbCp 2 F] 3 is trimeric with formal eight‐coordination for ytterbium and a planar (YbF) 3 ring, whereas [Yb(MeCp) 2 F] 4 is an eight‐coordinate tetramer having a puckered (YbF) 4 ring with F–Yb–F angles of ca. 90° and Yb–F–Yb angles close to 180° [178.9(4), 168.4(3)°]. Both [Yb(MeCp) 2 F(THF)] 2 and [YbCp 2 F(OPPh 3 )] 2 are nine‐coordinate fluoride‐bridged dimers.