324
N. Hidalgo et al.
Ti
O
PCy 2
BPh 4
Ti
O
PCy 2
O
O
Ph
Ph
Ph
Ph
BPh 4
Ph
Ph
O
Ti
O
PCy 2
BPh 4
O
Ph
PhCHO
1
2
3
Ti
Ph
Ph
PCy 2
BPh 4
Ti
Ph
Ph
PCy 2
BPh 4
O
Fc
Fe
O
CH 2 Cl 2, 25 ºC
4
5
(a)
(b)
+
Scheme 9.1 Titanium-based frustrated Lewis pairs reported by the group of Erker
Ti N
P
R
R
R
R
R=Ph,
i Pr
Ti NH
R
R
6
Ti O
N
R
R
P R
R
Ph
Ti NH
R
R P R
R
O
H
O
Ti N
Cl
7
8
9
HCCPh
Toluene
25 ºC
Toluene
25 ºC
Inactive
(a)
(b)
10, R = Et, CH 2 Ph
Ti O
N R
R
X = Cl, R' = CH 2 Cl
X = Cl, R' = CH 2 Ph
X = F, R' = C 10 H 21
Cl
R'
F
C 9 H 19
or
Toluene, 25 ºC
R'
(R' = Cl, Ph)
X
11
Scheme 9.2 C–H and C–halogen bond activation of electrophilic titanium complexes stabilized by
Cp-based tridentate ligands with pendant basic functionalities. The [BCH 3 (C 6 F 5 ) 3 ] − counteranion
has been omitted for clarity