Copyright WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001.
Supporting Information for Angew. Chem. Int. Ed. Z16217
Acetylenes Rearranging on RutheniumPorphyrinogen and Leading to Vinylidene and
Carbene Functionalities
Lucia Bonomo, Christine Stern, Euro Solari, Rosario
Scopelliti, and Carlo Floriani*
Synthesis of 3. PhCCH (0.28 g, 2.74 mmol) was added at
room temperature to an amber solution of 1⋅6(C4H10O2),
(3.05 g, 2.74 mmol) in THF (100 mL). The reaction mixture
was stirred overnight and then evaporated to dryness. nHexane (50 mL) was added to the residue to give a brown
solid which was collected and dried in vacuo (1.99 g, 90%).
Recrystallization from DME gave crystals suitable for X-Ray
diffraction.
H NMR (D6-DMSO, 400 MHz, 25 °C, TMS): δ = 6.49
1
(m, 2H: ArH), 6.24 (m, 1H; ArH), 5.71 (s, 8H; C4H2N
overlapping with m, 2H; ArH), 4.03 (s, 1H; CH), 3.86 (s, 6H;
DME), 3.20 (s, 9H; DME), 1.72 (s, 12H; CH3), 1.35 (s, 12H;
CH3); elemental analysis calcd (%) for 3⋅1.5(C4H10O2),
C42H53N4Na2O3Ru (809.0): C 62.36, H 6.60, N 6.93; found
C 61.80, H 6.69, N 7.05.
Synthesis of 4b. Method A. Na (61 mg, 2.65 mmol) and
naphthalene (170 mg, 1.32 mmol) were added to a solution of
2 2(C4H10O2) (2.06 g, 2.65 mmol); in THF (100 mL). The
reaction mixture was stirred overnight, was then evaporated
to dryness and the solid residue was treated with n-hexane
(50 mL) to give a white solid which was collected and dried
in vacuo (1.75 g, 74%) (ν C=C=C, 1828 cm-1). Crystals suitable
for X-ray diffraction were grown in DME. Elemental analysis
calcd (%) for 4⋅2(C4H10O2)⋅6(C4H8O), C92H134N10Na6O10Ru2 (1880.2):
C 58.77, H 7.18, N 7.45; found C 58.77, H 702, N 7.51.
Synthesis of 4b. Method B. Na (18 mg, 0.76 mmol) and
naphthalene (50 mg, 0.36 mmol) were added to a solution of
8⋅4(C4H10O2) (0.52 g, 0.38 mmol) in THF (100 mL). The reaction
mixture was stirred for 48 hours at room temperature. Then
it was evaporated to dryness and the solid residue treated
with n-hexane (50 mL) to give a white solid which was
collected and dried in vacuo (0.22 g, 69%). Crystals
suitable for X-ray diffraction were grown in DME. Elemental
analysis calcd (%) for 4⋅4(C4H10O2)⋅2(C4H8O), C84H122N10Na6O10Ru2
(1.772.0): C 56.94, H 6.94, N 7.90: found C 56.75, H 6.87,
N 7.87.
Synthesis of 5. MeOH (62 mg, 1.95 mmol) was added to a
solution of 2⋅2(C4H10O2) (1.52 g, 1.95 mmol) in THF (100 mL).
After one hour stirring
1
HNMR spectrum of the reaction
mixture showed that 2 was completely transformed into 5. The
reaction mixture was evaporated to dryness and the solid
residue was treated with n-hexane (50 mL) to give a yellow
solid which was collected and dried in vacuo (1.26 g, 75%).
Crystals suitable for X-ray diffraction were obtained in a
mixture THF/n-hexane.
1
H NMR (400 MHz, D6-benzene/D4-TDF,
25 °C, TMS): δ = 6.26 (s, 8H; C4H2N), 3.51 (m, 8H; THF), 3.29
(s, 4H; DME), 3.18 (s, 6H; DME), 3.10 (s, 3H; OCH3), 1.77(s,
3H; CH3), 1.71(s, 12H; CH3), 1.65 (s, 12H; CH3), 1.52 (m, 8H;
THF); elemental analysis calcd (%) for 5⋅1(C4H10O2)⋅2(C4H8O),
C43H64N4Na2O5Ru (864.0): C 59.77, H 7.47, N 6.48; found
C 59.81, H 7.54, N 6.38.
Synthesis of 6. A solution of PhSH (0.27 g, 2.26 mmol) in
THF (50 mL) was added dropwise to a solution of 2⋅4(C4H8O)
(2.0 g, 1.95 mmol) in THF (100 mL) at T = -60 °C. The
reaction mixture was slowly warmed at room temperature and
then the obtained red solution was evaporated to dryness.
The red-brown powder was collected with n-hexane (50 mL) and
dried in vacuo (1.56 g, 77%).
1
H NMR (400 MHz, D6-benzene/D4-
TDF, 25 °C, TMS): δ = 7.16 (m, 2H; ArH), 6.89 (m, 3H; ArH),
6.24 (s, 8H; C4H2N), 3.51 (m, 16H; THF), 1.77(s, 3H; CH3),
1.71(s, 12H; CH3), 1.65 (s, 12H; CH3), 1.52 (m, 16H; THF);
elemental analysis calcd (%) for 6⋅4(C4H8O), C52H72N4Na2O4RuS
(996.3): C 62.69, H 7.28, N 5.62; found C 62.81, H 7.34,
N 5.52
Synthesis of 7. H2O (36 mg, 1.95 mmol) was added to a
solution of 2⋅4(C4H8O) (2.0 g, 1.95 mmol) in THF (100 mL).
After 10 minutes stirring, the reaction mixture was
evaporated to dryness and the solid residue was treated with
n-hexane (50 mL) to give a brown solid, which was collected
and dried in vacuo (1.48 g, 95%). Crystals suitable for Xray diffraction were obtained from a mixture THF/dioxane. IR
(Nujol, ν max) = 1577cm-1; elemental analysis calcd (%) for
7⋅4(C4H8O), C46H67N4Na2O5Ru (903.1): C 61.18, H 7.48, N 6.20;
found C 60.91, H 7.54, N 6.17.
Figure S1. A plot of complex 4 showing the Na(THF)5+ cations [hydrogen atoms omitted for clarity].