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Synthesis, Structure, and Reactivity of the Sterically Crowded Complex (C 5 Me 4 SiMe 3 ) 3 U
Author(s) -
Siladke Nathan A.,
Ziller Joseph W.,
Evans William J.
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201000225
Subject(s) - steric effects , chemistry , reactivity (psychology) , cyclopentadienyl complex , ring (chemistry) , cationic polymerization , ligand (biochemistry) , stereochemistry , crystallography , yield (engineering) , medicinal chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology , catalysis , materials science , metallurgy
Abstract The unusual chemistry obtainable from sterically crowded (C 5 R 5 ) 3 M complexes has been explored with M = U and (C 5 Me 4 SiMe 3 ) 1– , a ligand that has independently provided unexpected uranium chemistry. (C 5 Me 4 SiMe 3 ) 2 UMe 2 ( 1 ), is reduced by potassium to generate the “ate” salt (C 5 Me 4 SiMe 3 ) 2 UMe 2 K ( 2 ), which reacts with [HNEt 3 ][BPh 4 ] to yield the cationic species [(C 5 Me 4 SiMe 3 ) 2 U][BPh 4 ] ( 3 ). KC 5 Me 4 SiMe 3 reacts with 3 in benzene to form (C 5 Me 4 SiMe 3 ) 3 U, ( 4 ). The structure of 4 shows that the displacement of the methyl groups from the cyclopentadienyl ring planes, a useful indicator of steric crowding, is the largest ever observed in a (C 5 R 5 ) 3 M complex. The reactivity of 4 is consistent with this structural indicator in that it engages in THF ring opening to form (C 5 Me 4 SiMe 3 ) 2 UO[(CH 2 ) 4 (C 5 Me 4 SiMe 3 )](THF).