Titanocene-Catalyzed Hydrosilylation of Imines: Experimental and Computational Investigations of the Catalytically Active Species.

Research output: Contribution to journalArticle

Abstract

The mechanistic studies of the asym. catalytic hydrosilylation of imines using (R,R)-ethylene-1,2-bis(η5-4,5,6,7-tetrahydro-1-indenyl)titanium (R)-1,1'-binaphth-2-olate (1) and (S,S)-ethylene-1,2-bis(η5-4,5,6,7-tetrahydro-1-indenyl)titanium dichloride (2) as catalyst precursors are reported. After activation with RLi (R = alkyl, aryl) and a silane, these complexes are known catalysts for hydrosilylation reactions. However, the exact nature of the catalytic active species is still a subject of debate and was therefore studied using exptl. (IR, NMR, EPR, GC/MS) and computational methods. The results indicate an EBTHITiRSiH2Ph compd. (EBTHI = ethylene-1,2-bis(η5-4,5,6,7-tetrahydro-1-indenyl), R = alkyl, aryl) as the catalytically active species. This Ti(IV) species is postulated to be responsible for the lower activities of 1 and 2 in contrast to hydrosilylations with ethylene-1,2-bis(η5-4,5,6,7-tetrahydro-1-indenyl)titanium difluoride (3), for which a Ti(III)-H compd. was postulated to be the active species. [on SciFinder(R)]
Original languageEnglish
Pages (from-to)2546-2553
Number of pages8
JournalOrganometallics
Volume28
Issue number8
DOIs
Publication statusPublished - 2009

Cite this