From Carbanions to Organometallic Compounds: Quantification of Metal Ion Effects on Nucleophilic Reactivities
The influence of the metal on the nucleophilic reactivities of indenyl metal compounds was quantitatively determined by kinetic investigations of their reactions with benzhydrylium ions (Ar2CH+) and structurally related quinone methides. With the correlation equation logk2=sN(N+E), it can be derived that the ionic indenyl alkali compounds are 1018 to 1024 times more reactive (depending on the reference electrophile) than the corresponding indenyltrimethylsilane. Different worlds: Kinetic investigations with reference electrophiles show that a reaction with an electrophile, which would proceed within milliseconds with indenyl lithium, would require much more than the age of the universe with the corresponding organosilicon compound. Met=metal.
Corral-Bautista, Francisco,Klier, Lydia,Knochel, Paul,Mayr, Herbert
supporting information
p. 12497 - 12500
(2015/10/12)
Fluxional behavior of group IV trimethylindenyl compounds
The indenyltrimethyl compounds of silicon, germanium, and tin have been investigated by variable-temperature proton magnetic resonance spectroscopy and shown to be fluxional molecules. For (CH3)3SnC9H7 the complete range from limiting high- to limiting low-temperature behavior was observed. The presence of tin to ring hydrogen coupling confirms the intramolecular nature of the rearrangement. Relative signs of the proton-proton and tin-proton coupling constants in (CH3)3SnC9H7 have been determined.
Rakita,Davison
p. 1164 - 1167
(2008/10/08)
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