Comp
lexes Ind
XTiC
l3 (
1,
2) react with 1.0, 2.0, and 3.0 equiv of MeMgC
l to give Ind
XTiMeC
l2 (
3,
4),Ind
XTiMe
2C
l (
5,
6), and Ind
XTiMe
3 (
7,
8), respective
ly (X = CH
2CH
2OMe (
1,
3,
5,
7), CH
2CH
2NMe
2(
2,
4,
6,
8)). Comp
lexes
3,
6, and
8 have been characterized by X-ray diffraction ana
lysis. The structuresprove that in the so
lid state the pendant substituents of the indeny
l ligands are coordinated to the meta
lcenter (
d(Ti-O) = 2.296(3) Å (
3);
d(Ti-N) = 2.4006(19) (
6), 2.4214(17) Å (
8)) disposed transoid to amethy
l ligand. In so
lution the pendant donor groups are invo
lved in coordination-dissociation equi
libria(
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 4.2 ± 0.6 kca
l mo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
= 15.5 ± 3 eu for
3;
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 3.4 ± 0.2 kca
l mo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
=11.6 ± 0.3 eu for
4;
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 3.5 ± 1.1 kca
l mo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
= 15.2 ± 4.4 eu for
5;
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 4.3 ± 1.3 kca
lmo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
= 16.0 ± 2.8 eu for
6;
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 2.2 ± 0.5 kca
l mo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
= 11.0 ± 2.2 eu for
7;
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
H![](/images/entities/deg.gif)
= 4.9 ± 0.5 kca
l mo
l-1 and
![](/images/gifchars/De<font color=)
lta.gif" BORDER=0 >
S![](/images/entities/deg.gif)
= 20.8 ± 2.2 eu for
8). Comp
lexes
7,
8, IndTiMe
3 (
9), and H
4IndTiMe
3(
10; H
4Ind = 4,5,6,7-tetrahydroindeny
l) are efficient cata
lyst precursors for the regiose
lective hydroamination of 1-octyne, pheny
lacety
lene, and 1-pheny
lpropyne with aromatic (2,6-dimethy
lani
line and 2,6-diisopropy
lani
line) and a
liphatic (
tert-buty
lamine, dodecy
lamine, and cyc
lohexy
lamine) amines. Thereactions give imine or imine-enamine mixtures, which are reduced to the corresponding secondaryamines. The Markovnikov or anti-Markovnikov nature of the obtained products depends on the a
liphaticor aromatic character of both the a
lkyne and the amine. Markovnikov products with regiose
lectivities of100% are formed from the reactions between 1-octyne and aromatic amines, whi
le anti-Markovnikovderivatives with regiose
lectivities of 100% are obtained from the reactions of aromatic a
lkynes with a
llthe studied amines and from the reactions of 1-octyne with
tert-buty
lamine and dodecy
lamine. The reactionsof 1-octyne with cyc
lohexy
lamine give mixtures of both types of products. A comparative study betweenthe cata
lytic efficiencies of
7-
10 and those of their cyc
lopentadieny
l counterparts is a
lso inc
luded (Tab
le4).