Donor-Acceptor Indenylruthenium(II) Complexes
Organometallics, Vol. 18, No. 4, 1999 595
2.2 Hz, H-2), 6.14 (d, 2H, J HH ) 2.2 Hz, H-1,3), 6.30 and 7.62
(d, 2H each one, J HH ) 8.7 Hz, C6H4NO2-4), 6.69-7.52 (m, 24H,
Ph, H-4,7 and H-5,6); 13C{1H} (CDCl3) δ 25.81 (m, P(CH2)2P),
79.75 (s, C-1,3), 97.96 (s, C-2), 113.23 (s, C-3a,7a), 115.36 (s,
Câ), 123.24, 123.52 and 124.96 (s, C-4,7, C-5,6 and CH of C6H4-
NO2-4), 129.16-133.43 (m, Ph and CH of C6H4NO2-4), 135.00
and 145.14 (s, C of C6H4NO2-4), 348.85 (t, 2J CP ) 16.5 Hz, Rud
CR); ∆δ(C-3a,7a) ) -17.47. For 2c. 49% (0.437 g). 834. Anal.
Calcd for RuC42H34F6P3O2N: C, 56.50; H, 3.83; N, 1.56.
Found: C, 55.92; H, 3.75; N, 1.48. 117. 31P{1H} (CDCl3) δ 1.69
) 2.3 Hz, H-1,3), 4.82 (t, 1H, J HH ) 2.3 Hz, H-2), 4.91 (d, 2H,
2J HP ) 14.5 Hz, CH2), 6.07 and 6.84 (m, 2H each one, H-4,7
and H-5,6), 7.07-8.06 (m, 45H, Ph); 13C{1H} ((CD3)2CO) δ
2
21.39 (d, J CP ) 54.2 Hz, CH2), 74.84 (s, C-1,3), 93.03 (d, J CP
) 12.2 Hz, Câ), 95.46 (s, C-2), 110.15 (s, C-3a,7a), 111.38 (m,
Ru-CR), 119.85-139.60 (m, Ph, C-4,7 and C-5,6); ∆δ(C-3a,-
7a) ) -20.55.
Syn th esis of [Ru {CtCCHdCH(CHdCH)n R}(η5-C9H7)-
(P P h 3)2] (n ) 0, R ) C6H4NO2-4 [(E,Z)-7a ], C4H2ONO2-2,3
[(E,Z)-8a ], C4H2SNO2-2,3 [(E)-8b], C6H4CN-4 [(E,Z)-13],
C5H4N-4 [(E)-16], C5H4F eC5H5 [(E)-18]; n ) 1, R ) C6H4-
NO2-4 [(EE,ZE)-7b]), a n d [Ru {CtCCHd(C6H4NO2-3)2}(η5-
C9H7)(P P h 3)2] (9). Gen er a l P r oced u r e. A solution of LinBu
(1.6 M in hexane, 0.625 mL, 1 mmol) was added to a solution
of [Ru{CtCCH2(PPh3)}(η5-C9H7)(PPh3)2][PF6] (6) (1.186 g, 1
mmol) in 25 mL of THF kept at -20 °C. After the addition
was complete, the color of the solution had changed from yellow
to violet. After stirring the resulting mixture for 15 min, the
corresponding aldehyde or ketone (3 mmol) was added and
stirred for 30 min after warming to room temperature. The
solvent was then removed in vacuo, and the solid residue was
transferred to an Alox I chromatography column. Elution with
hexane/diethyl ether (3/1) gave an orange band from which
the corresponding σ-enynyl complex was obtained by sol-
vent removal. Yield, IR (KBr, ν(CtC), ν(CtN), cm-1), and
analytical or mass spectral data (FAB m/e) are as follows. For
7a . 90% (0.822 g). 2034 (E and Z isomers). Anal. Calcd for
RuC55H43O2P2N: C, 72.35; H, 4.75; N, 1.53. Found: C, 71.89;
H, 4.96; N, 1.36. For 7b. 73% (0.685 g). 2033 (EE and ZE
isomers). Anal. Calcd for RuC57H45O2P2N: C, 72.91; H, 4.83;
N, 1.49. Found: C, 72.91; H, 4.88; N, 1.42. For 8a . 41% (0.370
g). 2027 (E and Z isomers). MS for RuC53H41O3P2N: [M+] )
903, [M+ - PPh3] ) 642. For 8b. 46% (0.423 g). 2021. MS for
RuC53H41O2P2NS: [M+] ) 919, [M+ - PPh3] ) 657. For 9. 88%
(0.909 g). 2034. Anal. Calcd for RuC61H46O4P2N2: C, 70.85; H,
4.48; N, 2.70. Found: C, 70.25; H, 4.82; N, 2.58. For 13. 71%
(0.634 g). 2041 (CtC, E and Z isomers), 2216 (CtN, E isomer),
2137 (CtN, Z isomer). Anal. Calcd for RuC56H43P2N: C, 75.32;
H, 4.85; N, 1.56. Found: C, 74.59; H, 5.01; N, 1.49. For 16.
83% (0.721 g). 2039. Anal. Calcd for RuC54H43P2N: C, 74.55;
H, 4.98; N, 1.61. Found: C, 73.95; H, 4.62; N, 1.58. For 18.
67% (0.654 g). 2048. Anal. Calcd for FeRuC59H48P2: C, 72.61;
H, 4.96. Found: C, 72.36; H, 4.93.
1
(s); H (CDCl3) δ 4.57 (s, 1H, RudCdCH), 4.74 and 5.10 (m,
1H each one, PCHaHbP), 5.86 (t, 1H, J HH ) 2.5 Hz, H-2), 6.33
(m, 4H, H-1,3 and H-4,7 or H-5,6), 7.10-7.44 (m, 24H, Ph,
H-4,7 or H-5,6 and C6H2H2NO2-4), 7.66 (d, 2H, J HH ) 8.6 Hz,
C6H2H2NO2-4); 13C{1H} (CDCl3) δ 45.62 (t, J CP ) 29.0 Hz,
PCH2P), 80.69 (s, C-1,3), 95.81 (s, C-2), 111.92 (s, C-3a,7a),
117.62 (s, Câ), 124.14, 124.61, 126.02 and 128.82 (s, C-4,7, C-5,6
and CH of C6H4NO2-4), 129.62-133.70 (m, Ph), 135.83 and
2
145.93 (s, C of C6H4NO2-4), 352.42 (t, J CP ) 14.7 Hz, Rud
CR); ∆δ(C-3a,7a) ) -18.78.
Syn th esis of [Ru (CtC-C6H4NO2-4)(η5-C9H7)L2] (L2
)
2P P h 3 (3a ), d p p e (3b), d p p m (3c)). Gen er a l P r oced u r e.
A solution of 2a -c (1 mmol) in 50 mL of dichloromethane was
treated with Al2O3 (1.019 g, 10 mmol), and the mixture was
stirred at room temperature for 1 h. The solution was then
evaporated to dryness, and the solid residue was extracted
with diethyl ether. The evaporation of the diethyl ether gave
3a -c as red solids. Yield, IR (KBr, ν(CtC), cm-1), and
analytical data are as follows. For 3a . 79% (0.701 g). 2051.
Anal. Calcd for RuC53H41P2O2N: C, 71.77; H, 4.66; N, 1.58.
Found: C, 70.95; H, 4.33; N, 1.62. For 3b. 68% (0.507 g). 2060.
Anal. Calcd for RuC43H35P2O2N: C, 67.88; H, 4.64; N, 1.84.
Found: C, 67.25; H, 4.58; N, 1.69. For 3c. 42% (0.314 g). 2052.
Anal. Calcd for RuC42H33P2O2N: C, 67.56; H, 4.45; N, 1.87.
Found: C, 66.97; H, 4.46; N, 1.80.
Syn th esis of [Ru (CtC-C6H4R-4)(η5-C9H7)(P P h 3)2] (R )
CtC-C6H4NO2-4 (4), NdCH-C6H4NO2-4 (5)). A mixture of
[RuCl(η5-C9H7)(PPh3)2] (1a ) (0.776 g, 1 mmol), NaPF6 (0.336
g, 2 mmol), and HCtC-C6H4R-4 (R ) CtC-C6H4NO2-4 or
NdCH-C6H4NO2-4) (2 mmol) in 50 mL of methanol was
heated under reflux for 30 min. The resulting solution was
evaporated to dryness, and the solid residue was dissolved in
dichloromethane (ca. 20 mL) and filtered into stirred diethyl
ether (ca. 100 mL) to give a brown solid precipitate. The
resulting solid was washed with diethyl ether (2 × 20 mL),
dissolved in dichloromethane (ca. 25 mL), and treated, at room
temperature, with Al2O3 (for complex 4; 1.019 g, 10 mmol) or
K2CO3 (for complex 5; 1.382 g, 10 mmol) for 1 h. The solution
was then evaporated to dryness, and the residue was extracted
with diethyl ether. The evaporation of the diethyl ether gave
4 and 5 as red solids. Yield, IR (KBr, ν(CtC), cm-1), and
analytical or mass spectral data (FAB m/e) are as follows. For
4. 60% (0.592 g). 2070, 2207. Anal. Calcd for RuC61H45P2O2N:
C, 74.22; H, 4.59; N, 1.41. Found: C, 73.85; H, 4.22; N, 1.30.
For 5. 51% (0.505 g). 2069. MS for RuC60H46P2O2N2: [M+] )
990, [M+-PPh3] ) 728.
Syn th esis of [Ru (CtN)(η5-C9H7)(P P h 3)2] (10). A mixture
of [RuCl(η5-C9H7)(PPh3)2] (1a ) (0.776 g, 1 mmol), and KCN
(0.260 g, 4 mmol) in 50 mL of methanol was heated under
reflux for 1 h. The resulting solution was concentrated (ca. 20
mL) to give, after cooling to -10 °C, yellow crystals of complex
10. Yield, IR (KBr, ν(CtN), cm-1), analytical, and NMR
spectroscopic data (ppm) are as follows. 81% (0.767 g). 2071.
Anal. Calcd for RuC46H37P2N: C, 72.05; H, 4.86; N, 1.82.
Found: C, 71.35; H, 4.91; N, 1.72. 31P{1H} (CD2Cl2) δ 51.94
1
(s); H (CD2Cl2) δ 4.57 (d, 2H, J HH ) 2.5 Hz, H-1,3), 5.17 (t,
1H, J HH ) 2.5 Hz, H-2), 6.45 and 6.90 (m, 2H each one, H-4,7
and H-5,6), 7.13-7.69 (m, 30H, Ph); 13C{1H} (CD2Cl2) δ 73.87
(s, C-1,3), 94.43 (s, C-2), 109.26 (s, C-3a,7a), 123.89 (s, C-4,7
or C-5,6), 127.45-137.61 (m, Ph and C-4,7 or C-5,6), 143.49
Syn th esis of [Ru {CtCCH2(P P h 3)}(η5-C9H7)(P P h 3)2][P F6]
(6). A mixture of [RuCl(η5-C9H7)(PPh3)2] (1a ) (0.776 g, 1 mmol),
NaPF6 (0.336 g, 2 mmol), HCtCCH2(OH) (0.118 mL, 2 mmol),
and PPh3 (2.622 g, 10 mmol) in 50 mL of methanol was stirred
at room temperature for 8 h. A yellow suspension was formed.
The solvent was then decanted, and the solid residue was
dissolved in dichloromethane (ca. 40 mL) and filtered over
kieselguhr. The resulting solution was evaporated to dryness,
and the yellow solid obtained was washed with diethyl ether
(2 × 20 mL) and vacuum-dried. Yield, IR (KBr, ν(PF6-),
ν(CtC), cm-1), analytical, and NMR spectroscopic data (ppm)
are as follows. 65% (0.771 g). 837, 2087. Anal. Calcd for
RuC66H54F6P4: C, 66.83; H, 4.59. Found: C, 67.11; H, 4.69.
31P{1H} ((CD3)2CO) δ 18.51 (t, 5J PP ) 4.6 Hz, CH2-PPh3), 51.32
(d, 5J PP ) 4.6 Hz, Ru-PPh3); 1H ((CD3)2CO) δ 4.40 (d, 2H, J HH
2
(t, J CP ) 22.7 Hz, Ru-CtN); ∆δ(C-3a,7a) ) -21.44.
Syn th esis of [(η5-C9H7)(P P h 3)2Ru {(µ-CtN)M(CO)5}] (M
) Cr (11a ), W (11b)), [(η5-C9H7)(P P h 3)2Ru {(µ-CtCCHd
CH-C6H4CtN-4)M(CO)5}] (M ) Cr [(E, Z)-14a ], W [(E, Z)-
14b]), a n d [(η5-C9H7)(P P h 3)2Ru {(µ-CtCCHdCH-C5H4N-
4)M(CO)5}] (M ) Cr [(E)-17a ], W [(E)-17b]). Gen er a l
P r oced u r e. A solution of 10, (E, Z)-13 or (E)-16 (1 mmol) in
25 mL of THF was treated with a THF solution of [M(CO)5-
(THF)] (M) Cr, W) (1 mmol), and the mixture was stirred at
room temperature for 1 h. The solution was then evaporated
to dryness, and the orange solid residue was washed with
hexane (ca. 10 mL). Yield, IR (KBr, ν(CtC), ν(CtO), ν(CtN),
cm-1), analytical, and NMR spectroscopic data (ppm) are as
follows. For 11a . 70% (0.678 g). 1884, 1930, 2064, 2109. Anal.