TY - JOUR
T1 - Titanocene-Catalyzed Hydrosilylation of Imines: Experimental and Computational Investigations of the Catalytically Active Species.
AU - Gruber-Woelfler, Heidrun
AU - Khinast, Johannes G.
AU - Flock, Michaela
AU - Fischer, Roland
AU - Sassmannshausen, Joerg
AU - Stanoeva, Tsvetanka
AU - Gescheidt-Demner, Georg
N1 - M1 - Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved.
CAPLUS AN 2009:358788(Journal)
PY - 2009
Y1 - 2009
N2 - 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)]
AB - 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)]
KW - reaction mechanism titanocene catalyzed asym hydrosilylation imine alkyllithium activation
U2 - 10.1021/om800643q
DO - 10.1021/om800643q
M3 - Article
SN - 0276-7333
VL - 28
SP - 2546
EP - 2553
JO - Organometallics
JF - Organometallics
IS - 8
ER -