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Stable and Catalytically Highly Active ansa Compounds with Cycloalkyl Moieties as Bridging Units
Author(s) -
Capapé Alejandro,
Raith Alexander,
Kühn Fritz E.
Publication year - 2009
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200800559
Subject(s) - chemistry , cyclooctene , thermogravimetric analysis , catalysis , medicinal chemistry , acetonitrile , molybdenum , alkyl , yield (engineering) , metal carbonyl , metal , solid state , stereochemistry , polymer chemistry , organic chemistry , materials science , metallurgy
The complexes Mo{η 5 ‐C 5 H 4 [CH(CH 2 ) 3 ]‐η 1 ‐CH}(CO) 3 ( 2a ) and W{η 5 ‐C 5 H 4 [CH(CH 2 ) 3 ]‐η 1 ‐CH}CO) 3 ( 2b ) were synthesized by reacting spiro[4.2]bicyclo[4.1]deca‐6,8‐diene ( 1 ) with the tri(acetonitrile)tri(carbonyl)metal complexes M(CO) 3 (CH 3 CN) 3 (M=Mo, W). Thermogravimetric (TGA) measurements confirm that the complexes are stable up to 140 °C in air in the solid state. The complexes 2a and 2b are very active catalysts at room temperature for the epoxidation of cyclooctene with tert ‐butyl hydroperoxide (TBHP) as oxidant, reaching TOFs of up to 3650 h −1 . Complex 2a achieves a quantitative product yield without formation of any by‐products within 1.5 h, outperforming previously published ansa compounds and performing on par with the cyclopentadienyltri(carbonyl)(halo)‐ or (alkyl)molybdenum compelxes CpMo(CO) 3 R (R=Hal, Me, Et).