ACCEPTED MANUSCRIPT
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Major isomer (presumably trans): δ = 9.16 (s, 2H), 9.02 (d, J = 9.4 Hz, 2H), 8.16-8.10 (m, 4H), 7.35 (d, J =
.0 Hz, 2H), 6.70 (m appear as s, 4H of the coordinated ring), 4.71 (s, 10H, Cp).
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Minor isomer (presumably cis): δ = 9.37 (s, 2H), 9.20-9.16 (m, 2H), 8.34-8.25 (m, 4H), 7.50 (d, J = 5.7 Hz,
2
H), 6.83-6.80 (m, 4H of the coordinated ring), 4.81 (s, 10H, Cp).
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C NMR (151 MHz, (CD ) CO): after recrystallization – only one isomer is detected: δ = 131.84, 131.04,
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29.42, 128.77, 125.60, 94.95, 93.75, 88.64, 88.05, 86.95, 82.15, 78.14 (Cp).
Elemental analysis (for crystals grown by slow diffusion of Et O vapors into solution of complex in
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nitromethane). Calculated for C H F Fe P ⋅CH NO : C, 45.50; H, 3.12; N, 1.61. Found: C, 45.91.; H,
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24 12
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.09; N, 1.09.
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.4. Synthesis of the complex [Cp*Ru(C H )]PF (2)
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The mixture of 1,2-dichloroethane (20 ml) and acetonitrile (0.2 ml) was heated to 60°C in a Schlenk tube
50 ml) under argon atmosphere. Then picene (5.6 mg, 0.020 mmol) was added and the mixture was
(
*
vigorously stirred for 1 hour until complete dissolution of ligand. After that [Cp Ru(MeCN) ]PF (10 mg,
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0
.020 mmol) was added to resulting solution and the mixture was stirred for additional 30 minutes. This
procedure (picene dissolution and complex addition) was repeated 3 times more. Then the reaction
mixture was heated up to 75°C and stirred for 3 days. The resulting brown solution was opened to air
and evaporated to dryness. The residue was dissolved in a small amount of nitromethane and the
solution was filtered through a short column (∼ 5 cm layer of Al O in Pasteur pipette). The solution was
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evaporated to a minimum amount (ca 0.5 ml) and added to the excess of Et O to precipitate the light
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grey product, which was dried in vacuum. The yield was 29 mg (56% yield).
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H NMR (400 MHz, CD NO ): δ = 8.98 (d, J = 9.1 Hz, 1H), 8.84 (d, J = 9.6 Hz, 1H), 8.80 (d, J = 8.0 Hz, 1H),
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.62 (d, J = 9.2 Hz, 1H), 8.47 (d, J = 9.0 Hz, 1H), 8.03 (d, J = 9.2 Hz, 1H), 8.00 (d, J =7.6 Hz, 1H), 7.76 (t,
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J = 7.0 Hz, 1H), 7.71 (t, J = 7.3 Hz, 1H), 7.48 (d, J = 9.5 Hz, 1H), 7.12 (d, J = 6.2 Hz, 1H of the
coordinated ring), 6.43-6.37 (m, 1H of the coordinated ring), 6.10-5.96 (m, 2H of the coordinated ring),
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.40 (s, 15H, Cp*).
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C NMR (101 MHz, CD NO ): δ = 133.87, 131.86, 131.43, 131.26, 130.36, 130.31, 129.99, 129.44,
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29.20, 128.78, 127.71, 126.29, 125.44, 124.88, 123.10, 122.59, 96.21 (C Me ), 96.13, 95.24, 89.63,
5 5
9.35, 87.41, 82.10, 9.95 (C Me ).
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Elemental analysis (for crystals grown by slow diffusion of C H vapors into the solution of complex in
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(
CH ) CO). Calculated for C H F PRu: C, 58.27; H, 4.43. Found: C, 57.71; H, 4.50.
3 2 32 29 6
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.5. Synthesis of the complex [(Cp*Ru) (C H )](PF ) (3)
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A mixture of [Cp*Ru(MeCN) ]PF (76 mg, 0.15 mmol) and picene (14 mg, 0.05 mmol) in 1,2-
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dichloroethane (2.5 ml) was stirred at 75°C for 50 hours. The mixture was then opened to air and
evaporated The residue was dissolved in a small amount of nitromethane and the solution was filtered
through a short column (∼ 5 cm layer of Al O in Pasteur pipette). The solution was evaporated to a
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minimum amount (ca 0.5 ml) and added to the excess of Et O to precipitate the grey solid. It was
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