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M.D. Mbaye et al. / Journal of Organometallic Chemistry 690 (2005) 2149–2158
recrystallization. 1H NMR (C6D6, d, ppm): 1.30 (s, 15H,
C5Me5), 1.44 (s, 9H, But), 1.71 (s, 6H, 2Me), 2.24 (s, 6H,
2Me), 2.84 (s, 6H, 2Me), 6.76 (s, 2H, C6H2), 6.97 (s, 2H,
C6H2), 7.70 (s, 2H, CH@N); 13C{1H} NMR (CD2Cl2, d,
Calc. for C38H44N2Ru (629.85): C, 72.46; H, 7.04; N
4.45.
5.12. Synthesis of [(C5Me5)(Pri–N@CH–CH@N–Pri)-
(PMe3)Ru](PF6) (10a)
ppm): 9.0 (C5Me ), 18.0 (Me), 20.8 (Me), 20.9 (Me),
5
29.2 (C Me3), 33.3 (CMe3), 94.3 (C5Me5), 102.2
(RuC„C), 121.4 (RuC„C), 127.6 (CH), 129.3 (CH),
130.2 (C Me), 132.7 (CMe), 134.4 (C Me), 150.6
(CH@N), 151.6 (CN). Anal. Found: C, 70.84; H, 8.00;
N, 4.48%. Calc. for C36H48N2Ru (609.86): C, 70.90;
H, 7.93; N, 4.59.
A 1.0 M solution of PMe3 in THF (3.50 mL,
3.50 mmol) was added to a solution of 6a (1.27 g,
2.26 mmol) in methanol (30 mL), and the mixture was
stirred for 2 h. The solution was then evaporated under
vacuum and the residue was recrystallized from a dichlo-
romethane (20 mL)/diethyl ether (100 mL) mixture to
obtain green–black crystals. Yield: 1.28 g, 95%. 1H
5.10. Synthesis of (C5Me5)(Pri–N@CH–CH@N–Pri)-
Ru–CC–Ph (9a)
2
NMR (CD2Cl2, d, ppm): 1.18 (d, JPH = 8.8 Hz, 9H,
PMe3), 1.40 (d, 3J = 6.6 Hz, 6H, 2CHMe), 1.55 (d,
4
Complex 9a was similarly prepared starting from 6a
and phenylacetylene and was obtained as a dark or-
ange–brown crystalline solid after a slow evaporation
of the solution of the crude product in a mixture of
dichloromethane and hexane. Complex 9a was too solu-
3J = 6.8 Hz, 6H, 2CHMe), 1.79 (d, JPH = 0.9 Hz, 15H,
4
C5Me5), 4.46 (m, 2H, CHMe), 8.34 (d, JPH = 3.3Hz,
CH@N); 31P{1H} NMR (CD2Cl2, d, ppm): ꢀ3.2 (s),
ꢀ143.2 (sept, PF6); 13C{1H} NMR (CD2Cl2, d, ppm):
1
10.5 (C5Me5), 15.2 (d, JPC = 29.7 Hz, PMe3), 24.5
1
ble to allow further recrystallization. H NMR (CDCl3,
(CHMe), 24.9 (CHMe), 63.9 (C HMe2), 92.3 (C5Me5),
153.9 (d, JPC = 2.1 Hz, CH@N). Anal. Found: C,
d, ppm): 1.50 (d, 3J = 7.0 Hz, 6H, 2CHMe), 1.54 (d,
3J = 6.6 Hz, 6H, 2CHMe), 1.82 (s, 15H, C5Me5), 4.51
(m, 2H, CHMe), 6.86–7.08 (m, 5H, Ph), 8.10 (s, 2H,
CH@N); 13C{1H} NMR (CD2Cl2, d, ppm): 10.5
(C5Me5), 23.5 (CHMe), 24.9 (CHMe), 63.0 (CHMe2),
92.0 (C5Me5), 111.2 (RuC„C–C), 123.6 (Ph, para),
127.1 (RuC„C–C), 128.0 (Ph, CH), 130.5 (RuC„C–
C), 130.8 (Ph, CH), 145.8 (CH@N). Anal. Found: C,
65.15; H, 7.52; N, 5.58%. Calc. for C26H36N2Ru
(477.66): C, 65.38; H, 7.60; N, 5.86.
3
41.94; H, 6.68; N, 4.68; P, 10.39%. Calc. for
C21H40F6N2P2Ru (597.57): C, 42.21; H, 6.75; N, 4.69;
P, 10.37.
5.13. Synthesis of [(C5Me5)(Mes-N@CH–CH@N-Mes)-
(PMe3)Ru](PF6) (10b)
A 1.0 M solution of PMe3 in THF (2.70 mL,
2.70 mmol) was added to a cold mixture of 3b (1.00 g,
1.77 mmol), KPF6 (0.35 g, 1.90 mmol), and methanol
(30 mL). The mixture was stirred for 2 h at room temper-
ature and the resulting purple mixture was evaporated
under vacuum. The residue was extracted with dichloro-
methane (20 mL) and mineral salts were removed by fil-
tration. The filtrate was then covered with diethyl ether
(120 mL) to afford green–black crystals. Yield: 0.97 g,
73%. 1H NMR (CD2Cl2, d, ppm): 1.28 (d, 4JPH = 1.3 Hz,
15H, C5Me5), 1.46 (d, 2JPH = 8.9 Hz, 9H, PMe3), 1.93 (s,
6H, Me), 2.24 (s, 6H, Me), 2.36 (s, 6H, Me), 7.02 (m, 4H,
5.11. Synthesis of (C5Me5)(Mes-N@CH–CH@N-Mes)-
Ru–CC–Ph (9b)
A mixture of 6b (0.76 g, 1.00 mmol), phenylacetylene
(1.00 mL, an excess), K2CO3 (1.00 g, an excess) and
dichloromethane (30 mL) was stirred for 2 days and
the resulting mixture was filtered. The dark-orange fil-
trate was evaporated under vacuum to leave the product
1
as a violet solid that was found pure by H NMR spec-
4
troscopy. Dark-violet crystals were obtained in a moder-
ate yield (29%) by cooling the solution of the product in
a dichloromethane (20 mL)/hexane (120 mL) mixture.
Note that solutions of the product in acetone or haloge-
CH), 8.35 (d, JPH = 4.0 Hz, 2H, CH@N); 31P{1H}
NMR (CD2Cl2, d, ppm): ꢀ9.2 (s), ꢀ143.3 (sept, PF6);
13C{1H} NMR (CD2Cl2, d, ppm): 9.7 (C5Me5), 15.4 (d,
1JPC = 30.5 Hz, PMe3), 20.0 (Me), 20.8 (2Me), 95.5
(C5Me5), 128.1 (C Me), 129.8 (CH), 130.0 (CH), 130.7
(CMe), 137.4 (CMe), 149.7 (CN), 160.5 (d,
3JPC = 3.2 Hz, CH@N). Anal. Found: C, 52.61; H,
6.49; N, 3.79; P, 8.30%. Calc. for C33H48F6N2P2Ru
(749.77): C, 52.86; H, 6.45; N, 3.74; P, 8.26.
1
nated solvents are orange whereas the solid is violet. H
NMR (CDCl3, d, ppm): 1.26 (s, 15H, C5Me5), 1.75 (s,
6H, 2Me), 2.33 (s, 6H, 2Me), 2.62 (s, 6H, 2Me), 6.85
(s, 2H, C6H2), 6.95 (s, 2H, C6H2), 7.00–7.20 (m, 5H,
Ph), 8.04 (s, 2H, CH@N); 13C{1H} NMR (CD2Cl2, d,
ppm): 9.0 (C5Me5), 18.1 (Me), 20.1 (Me), 20.9 (Me),
95.0 (C5Me5), 114.8 (RuC„C–C), 124.2 (Ph, para),
127.1 (RuC„C–C), 127.9 (Ph, CH), 128.1 (Ph, CH),
129.5 (CH), 130.1 (CMe), 130.4 (RuC„C–C), 130.8
(CH), 132.1 (CMe), 134.8 (CMe), 151.3 (CN), 151.9
(CH@N). Anal. Found: C, 72.04; H, 7.00; N, 4.38%.
5.14. Synthesis of [(C5Me5)(Pri–N@CH–CH@N–Pri)-
(Ph2POMe)Ru](PF6) (11a)
A mixture consisting of a sample of 3a (1.00 g,
2.43 mmol), Ph2POMe (0.50 mL, 2.49 mmol), KPF6