Synthesis of the ligand of the complex 4.
(3-benzyl-1H-inden-1-yl)(2-methylbenz[e]-1H-inden-1-yl)dimethylsilane 31 ml (50 mmol, 1,6M in
hexane) n-Buthyl lithium was added to 9,0 ml (50 mmol) benzindene (2b) in 150 ml diethyl ether at 0
C. Reaction mixture was stirred at room temperature for 2 hours. 14,8 g (50 mmol) (3benzylindenyl)(chloro)dimethylsilane (2a) in 40 ml diethyl ether was added to cooled, 0 C, li-salt
solution. After over night stirring at RT reaction mixture was quenched with 150 ml saturated solution
of NH4Cl. Organic layer was separated after 20 minutes, dried with NaSO4(s) and evaporated to
constant weight. Product (yellow viscous oil) was purified by column chromatography using
toluene:hexane (1:4) mixture as an eluent. Yield was 10 g (48 %). 13C NMR could not be interpreted
due to overlapping peaks of the diastereomers. 1H NMR (CHCl3):  8.02 (d, 1H, Ar), 7.79 (d, 1H, Ar),
7.52-7.03 (m, 12H, Ar and 1H, CpInd), 6.05/6.00 (s, 1H, CpInd / s, 1H, CpInd), 3.82 (d, 2H, CH2), 3.67 (s,
1H, Cpaliphatic), 3.56/3.47 (s, 1H, Cpaliphatic / s, 1H, Cpaliphatic), 2.28/2.22 (s, 3H, CH3 / s, 3H, CH3), -0.21,
-0.27, -0.49, -0.51 (s, 3H, SiCH3 and s, 3H, SiCH3 / s, 3H, SiCH3 and s, 3H, SiCH3). MS(EI+): 442
(35), 263 (55) and 237 (100).
Synthesis of the complex 4.
Dimethylsilyl(3-benzylindenyl)(2-methylbenz[e]indenyl)zirconium dichloride 15 ml (23.9 mmol,
1,6M in hexane) of n-Buthyl lithium was added drop wise to pre-cooled (0 C) solution of 5,3 g (12
mmol) (3-benzylindenyl)(2-methyl-benzindenyl)dimethylsilane (2c) in 150 ml diethyl ether. Stirring
was continued for 2 hours in room temperature. Diethyl ether was removed. Pre-cooled (-78 C)
precipitate and 150 ml (-78 C) dichloromethane were combined. Temperature of the mixture had
stabilized to -78 C, 2.8 g (12 mmol) zirconium tetrachloride was added and reaction mixture was
allowed to warm up to room temperature. Reaction mixture was filtered after stirring it over night at
room temperature and evaporated in vacuo. After recrystallation from toluene-hexane mixtures mesolike isomer was obtained as yellow powder and yield was 1,1 g (15 %). 4 1H NMR (CHCl3): 7.95 (d,
3
JHH = 7.33 Hz, 1H), 7.59-7.23 (m, 7H), 7.16-7.01 (m, 7H), 6.80 (m, 1H), 5.76 (s, 1H), 4.12 (AB, 2JHH
= 19.05 Hz, 2H), 2.26 (s, 3H),1.34 (s, 3H,), 0.97 (s, 3H). MS(EI+): 602 (100), 567 (90), 237 (40).
HRMS(EI+) m/z for C32H28Cl2SiZr: observed 600.0370; error -2,4 ppm.
VCH synthesis
Vinylcyclohexane (2) was synthesized by elimination of water from 2-cyclohexylethanol (1) in the
presence of Al2O2/NaO catalyst according to the following reaction:
OH
Al 2O3
350- 450
( 1)
+
oC
H 2O
( 2)
The reaction was performed in tube oven reactor at temperature of ca. 350-400oC by continuous feed of
preheated (200oC) mixture of N2 gas and vaporized 2-cyclohexylethanol. The catalyst, impregnated on
the quartz wool, was inserted at the bottom of the reactor as a bed about 5 cm of thickness. After the
reaction the water and organic phases were separated and the organic part was dried with NaSO4
column. Final purification of vinylcyclohexane was done by fraction distillation resulting to 98.5 %
pure vinylcyclohexane.