Article
Organometallics, Vol. 28, No. 15, 2009 4429
(m, 1H; CH2N), 3.05 (m, 1H; CH2P), 2.85 (m, 1H; CH2P), 2.34
(s, 3H; CH3), 2.10-1.50 (m, 5H; CH2), 1.72 (s, 3H; CH3CO),
1.41 (br s, 1H; NH2), 0.84 (m, 1H; CH2). 13C{1H} NMR (50.3
MHz, C6D6, 20 °C): δ 183.4 (dd, 2J(C,P)=16.0, 8.3 Hz; CRu),
181.5 (s, CORu), 163.9 (s; NCC), 159.3 (s; NCCH2), 148.8-
(d, 2J(PP)=36.9 Hz). 19F{1H} NMR (188.3 MHz, C6D6, 20 °C):
δ -138.9 (s).
Synthesis of 9. The preparation of 9 was carried out in a
way similar to that described for 8, using compound 1 (100 mg,
0.131 mmol), 2.0 mL of a 2-propanol solution of NaOiPr (0.1 M,
0.200 mmol), and 3,30-dinitrobenzophenone (40 mg, 0.147 mmol),
resulting in a dark yellow product. Yield: 121 mg (92%). Anal.
Calcd for C54H50N4O5P2Ru: C, 64.99; H, 5.05; N, 5.61. Found:
C, 64.93; H, 5.01; N, 5.58. 1H NMR (200.1 MHz, C6D6, 20 °C): δ
8.47 (s, 1H; aromatic proton). 7.93 (m, 5H; aromatic protons),
7.57 (td, J(HH)=7.9, 1.8 Hz; 2H; aromatic protons), 7.45 (dd,
J(HH)=7.9, 1.8 Hz, 1H; aromatic proton), 7.40-6.85 (m, 14H;
aromatic protons), 6.78 (td, J(HH)=7.2, 1.3 Hz, 2H; aromatic
protons), 6.59 (t, J(HH)=7.8 Hz, 2H; aromatic protons), 6.40
(m, 2H; aromatic protons), 6.23 (m, 2H; aromatic protons), 5.88
(t, J(HH)=8.0 Hz, 2H; aromatic protons), 5.53 (d, J(HH)=6.8 Hz,
1H; aromatic proton), 5.20 (d, J(HP)=3.1 Hz, 1H; OCH), 4.69
(br s, 1H; NH2), 3.19 (m, 2H; CH2N, CH2P), 2.84 (m, 2H;
CH2N, CH2P), 2.35 (s, 3H; CH3), 2.03 (m, 2H; CH2), 1.85-1.15
(m, 5H; CH2, NH2). 13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ
186.9 (m; CRu), 163.9 (s; NCC), 157.2 (s; NCCH2), 157.1 (s;
C-NO2), 154.8 (d, J(C,P)=3.0 Hz; C-NO2), 149.1-115.0 (m;
aromatic carbon atoms), 80.3 (s, OCH), 52.2 (d, 3J(C,P) =
2.7 Hz; CH2N), 32.5 (m; CH2P), 31.8 (m; CH2P), 26.9 (s;
CH2), 23.0 (s; CH2), 22.3 (s, CH3). 31P{1H} NMR (81.0 MHz,
3
115.4 (m; aromatic carbon atoms), 52.7 (d, J(C,P)=2.8 Hz,
1
1
CH2N), 31.6 (d, J(C,P)=24.6 Hz; CH2P), 31.3 (d, J(C,P)=
31.9 Hz; CH2P), 26.2 (s; CH2), 25.9 (d, 4J(C,P) = 3.7 Hz;
CH3CO), 22.2 (s; CH2), 22.1 (s, CH3). 31P{1H} NMR (81.0 MHz,
2
2
C6D6, 20 °C): δ 60.8 (d, J(PP)=38.3 Hz), 44.6 (d, J(PP)=
38.3 Hz). IR (Nujol): ν 1713 cm-1 (asymmetric ν(OCO)).
Synthesis of 7. To a suspension of complex 1 (105 mg, 0.138
mmol) in toluene (2.1 mL) was added 2.1 mL of a 2-propanol
solution of NaOiPr (0.1 M, 0.21 mmol), and the mixture was
stirred at 60 °C for 2 h. The mixture was kept at -20 °C over-
night, affording the precipitation of NaCl, which was eliminated
by filtration on Celite. The compound 4-nitrophenol (21 mg,
0.151 mmol) was added, and the red solution was stirred for 1 h
at room temperature. The solvent was eliminated, toluene
(2 mL) was added, and the mixture was kept at -20 °C for 2 h.
After filtration on Celite, the resulting solution was concen-
trated (1 mL), and addition of pentane (10 mL) afforded a red-
orange product which was filtered and dried under reduced
pressure. Yield: 104 mg (87%). Anal. Calcd for C47H45N3O3-
P2Ru: C, 65.42; H, 5.26; N, 4.87. Found: C, 65.33; H, 5.37; N,
4.82. 1H NMR (200.1 MHz, C6D6, 20 °C): δ 8.16 (ddd, J(HH)=
9.7, 7.7, 2.0 Hz, 2H; aromatic protons), 8.0 (d, 3J(HH)=9.3 Hz,
2H; aromatic protons), 7.73 (m, 3H; aromatic protons), 7.45-
6.90 (m, 13H; aromatic protons), 6.64 (t, J(HH)=7.4 Hz, 1H;
aromatic proton), 6.45 (t, J(HH)=8.6 Hz, 2H; aromatic protons),
6.37 (t, J(HH)=8.8 Hz, 2H; aromatic protons), 6.00 (t, J(HH)=
2
2
C6D6, 20 °C): δ 57.3 (d, J(PP)=34.9 Hz), 40.4 (d, J(PP)=
34.9 Hz). IR (Nujol): ν 1526 (asymmetric ν(NO2)), 1352 cm-1
(symmetric ν(NO2)).
Synthesis of 10. The complex 1 (100 mg, 0.132 mmol) and
NaOSiMe3 (19 mg, 0.169 mmol) were suspended in toluene
(2 mL), and the mixture was stirred at room temperature for 1 h.
The suspension was kept at -20 °C overnight and filtered on
Celite, and the solution was concentrated (1 mL). Addition of
pentane (5 mL) afforded an orange precipitate, which was
filtered, washed with pentane (2 ꢀ 2 mL), and dried under
reduced pressure. Yield: 80 mg (74%). Anal. Calcd for C44H50-
N2OP2RuSi: C, 64.92; H, 6.19; N, 3.44. Found: C, 65.20; H,
3
8.1 Hz, 2H; aromatic protons), 5.92 (d, J(HH)=9.3 Hz, 2H;
aromatic protons), 5.79 (d, J(HH)=7.5 Hz, 1H; aromatic proton),
3.50 (m, 1H; NH2), 3.35-2.80 (m, 4H; CH2N and CH2P), 2.27
(s, 3H; CH3), 2.30-0.80 (m, 7H; CH2, NH2). 13C{1H} NMR
2
(50.3 MHz, C6D6, 20 °C): δ 182.6 (dd, J(C,P)=17.1, 7.5 Hz;
CRu), 177.9 (s; C-O), 163.9 (s; NCC), 156.6 (s; NCCH2),
149.4-115.4 (m; aromatic carbon atoms), 51.8 (d, 3J(C,P) =
2.8 Hz; CH2N), 31.0 (d, 1J(C,P) = 25.1 Hz; CH2P), 30.9 (d,
1J(C,P) = 32.2 Hz; CH2P), 26.6 (s; CH2), 22.1 (d, 2J(C,P) =
1.5 Hz; CH2), 22.0 (s, CH3). 31P{1H} NMR (81.0 MHz, C6D6,
20 °C): δ 62.1 (d, 2J(PP)=38.5 Hz), 41.6 (d, 2J(PP)=38.5 Hz). IR
(Nujol): ν 1495 (asymmetric ν(NO2)), 1342 cm-1 (symmetric
ν(NO2)).
1
5.93; N, 3.47. H NMR (200.1 MHz, C6D6, 20 °C): δ 8.43 (t,
J(HH)=8.0 Hz, 2H; aromatic protons), 7.94 (t, J(HH)=7.6 Hz,
2H; aromatic protons), 7.84 (s, 1H; aromatic proton), 7.41-6.58
(m, 16H; aromatic protons), 6.50 (t, J(HH)=6.2 Hz, 2H; aromatic
protons), 6.02 (m, 3H, aromatic protons), 4.50 (broad s, 1H;
NH2), 3.32 (m, 2H; CH2), 2.95 (m, 2H; CH2), 2.30 (s, 3H; CH3),
2.12-0.87 (m, 7H; CH2 and NH2), -0.17 (s, 9H; SiMe3).
13C{1H} NMR (50.3 MHz, C6D6, 20 °C): δ 185.0 (dd, 2J(C,P)=
15.9, 8.4 Hz; CRu), 164.4 (s; NCC), 156.9 (s; NCCH2), 149.3-
Synthesis of 8. To a suspension of 1 (148 mg, 0.195 mmol) in
toluene (3 mL) was added 3 mL of a 2-propanol solution of
KOiPr (0.1 M, 0.300 mmol), and the mixture was stirred at 60 °C
for 2 h. The suspension was kept at -20 °C for 2 h and KCl was
eliminated by filtration on Celite. 4-Fluoro-3-methylphenol
(31 μL, 0.279 mmol) was added, and the solution was stirred
for 30 min at room temperature. The solvent was eliminated,
and the residue was dissolved in toluene (2 mL). Evaporation of
the solvent afforded an orange solid which was dried under
reduced pressure. Yield: 150 mg (91%). Anal. Calcd for C48H47F-
N2OP2Ru: C, 67.83; H, 5.57; N, 3.30. Found: C, 68.01; H, 5.39;
N, 3.12. 1H NMR (200.1 MHz, C6D6, 20 °C): δ 8.61 (t, J(HH)=
8.1 Hz, 2H; aromatic protons), 8.07 (t, J(HH) = 8.1 Hz, 2H
aromatic protons), 7.85 (s, 1H; aromatic proton), 7.54-6.40 (m,
21H; aromatic protons), 6.15 (t, J(HH)=7.9 Hz, 2H; aromatic
protons), 5.90 (d, J(HH)=7.0 Hz, 1H; aromatic proton), 4.47
(broad s, 1H; NH2), 3.45-2.80 (m, 5H; CH2N, CH2P), 2.30
3
115.1 (m; aromatic carbon atoms), 51.8 (d, J(C,P)=2.7 Hz;
1
1
CH2N), 31.3 (d, J(C,P)=23.6 Hz; CH2P), 30.8 (d, J(C,P)=
29.5 Hz; CH2P), 27.0 (s; CH2), 22.3 (s; CH2), 22.1 (s; CH3), 4.8
(s; SiMe3). 31P{1H} NMR (81.0 MHz, C6D6, 20 °C): δ 59.3
(d, 2J(PP)=36.5 Hz), 39.8 (d, 2J(PP) = 36.5 Hz).
Synthesis of 11. Complex 1 (154 mg, 0.203 mmol) was
dissolved in dichloromethane (5 mL), and CF3SO3Tl (72 mg,
0.204 mmol) was added. The orange suspension was stirred at
room temperature for 2 h and filtered on Celite to eliminate
TlCl, and the filtrate was reduced to 1 mL. Addition of pentane
afforded a yellow precipitate, which was filtered, washed with
pentane, and dried under reduced pressure. Yield: 142 mg
(80%). Anal. Calcd for C42H41F3N2O3P2RuS: C, 57.73; H,
4.73; N, 3.21. Found: C, 57.65; H, 4.89; N, 3.01. 1H NMR
(200.1 MHz, CD2Cl2, 20 °C): δ 7.91 (m, 2H; aromatic protons),
7.60-7.20 (m, 16H; aromatic protons), 7.06 (d, J(HH)=8.0 Hz,
2H; aromatic protons), 6.83 (d, J(HH)=7.7 Hz, 2H; aromatic
protons), 6.73 (d, J(HH)=7.5 Hz, 2H; aromatic protons), 6.06
(m, 2H; aromatic protons), 4.18 (m, 1H; NH2), 3.81 (m, 1H;
CH2N), 3.61 (m, 1H; CH2N), 3.05 (m, 2H; PCH2), 2.20 (s, 3H;
CH3), 2.30-0.80 (m, 7H; NH2 and CH2). 13C{1H} NMR
(50.3 MHz, CD2Cl2, 20 °C): δ 178.1 (t, 2J(C,P)=12.6 Hz; CRu),
164.8 (s; NCC), 158.7 (s; NCCH2), 149.7-116.4 (m; aro-
4
(s, 3H; CH3), 2.05 (d, J(HF)=1.5 Hz, 3H; FCCCH3), 2.24-
1.01 (m, 6H; NH2, CH2). 13C{1H} NMR (50.3 MHz, C6D6,
20 °C): δ 185.4 (dd, 2J(C,P)=16.0, 7.8 Hz; CRu), 164.0 (s; NCC),
156.4 (s; NCCH2), 152.5 (d, 1J(CF)=220.6 Hz; C-F), 148.7-
3
114.9 (m; aromatic carbon atoms), 52.0 (d; J(C,P)=2.8 Hz,
1
1
CH2N), 31.4 (d, J(C,P)=30.0 Hz; CH2P), 30.6 (d, J(C,P)=
25.1 Hz; CH2P), 26.9 (s; CH2), 22.2 (s; CH2), 22.0 (s;
CH3), 15.0 (d, 3J(CF) = 1.6 Hz; FCCCH3). 31P{1H} NMR
2
1
(81.0 MHz, C6D6, 20 °C): δ 60.4 (d, J(PP) = 36.9 Hz), 38.6
matic carbon atoms), 119.8 (q, J(CF)=320.0 Hz; CF3), 52.9