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- W2082978402 abstract "Singly tucked-in titanocene [Ti(III)(η 5 -C 5 Me 5 )(η 5 :η 1 -C 5 Me 4 CH 2 )] ( 1 ) reacted readily with di- tert -butyl ketone and 2,4,6-trimethylacetophenone to give permethyltitanocene derivatives [Ti(III)(η 5 -C 5 Me 5 ){η 5 -C 5 Me 4 CH 2 C( t -Bu) 2 O-κ O }] ( 2 ) and [(Ti(III)(η 5 -C 5 Me 5 )-{η 5 -C 5 Me 4 CH 2 CMe(C 6 H 2 Me 3 )O-κ O }] ( 3 ) with the tetramethylcyclopentadienyl ring tethered to the titanium atom by ethoxy group disubstituted at C α . Crystal structures of 2 and 3 showed that the Ti–O bond is only slightly inclined to the tethered cyclopentadienyl ligand, and the bulky mesityl or tert -butyl substituents did not impose an observable steric hindrance into molecules of 2 and 3 . Whereas the Ti–O bond lengths in 2 and 3 do not significantly differ, a higher wavenumber of the 1a 1 → b 2 electronic transition for 2 (7326 cm –1 ) compared with that for 3 (6666 cm –1 ) indicates a more efficient oxygen-to-titanium π-electron back donation in 2 . This is induced by two electron-donating tert -butyl groups on C α compared with a combined effect of electron-donating methyl and electron-attracting mesityl substituents in 3 ." @default.
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- W2082978402 date "2009-01-01" @default.
- W2082978402 modified "2023-10-08" @default.
- W2082978402 title "Intramolecular alkoxide-tethered permethyltitanocene(III) complexes – synthesis and crystal structure" @default.
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- W2082978402 doi "https://doi.org/10.1135/cccc2008212" @default.
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