Organometallics
Article
and the reaction mixture was heated to 110 °C for 16 h. The mixture
was then layered with cyclohexane (5 mL) to yield X-ray-quality dark
red crystals (0.170 g, 63%).
3H, Ind). 31P{1H} NMR (C6D5Br): 34.4 (s, PPh3). 27Al NMR
(C6D5Br): no signal observed. 19F NMR (C6D5Br): −121.15 (br m,
12F, o-C6F5), −154.00 (br m, 6F, p-C6F5), −162.31 (br m, 12F, m-
C6F5). 13C{1H} NMR (partial, C6D5Br): 177.54 (s, CO2),151.32 (m,
Ph), 148.76 (m, Ph), 142.29 (m, Ph), 139.89 (m, Ph), 138.04 (m, Ph),
135.50 (m, Ph), 134.01 (m, Ph), 133.67 (m, Ph), 133.19 (m, Ph),
132.56 (HSQC, Ind), 131.96 (s, Ph), 131.77 (s, Ph), 131.55 (s, Ph),
128.93 (m, Ph), 128.45 (m, Ph), 128.04 (HSQC, Ind), 127.97
(HSQC, Ind), 127.06 (s, Ph), 123.39 (s, Ph), 123.16 (HSQC, Ind),
121.57 (s, Ph), 119.12 (s, Ph), 99.99 (s, Ph), 97.57 (s, Ph), 80.77
(HSQC, Ind). Anal. Calcd for C90H42Al2F30O2P2Ru·C6H12 (2026.41):
C, 56.90; H, 2.69. Found: C, 57.14; H, 3.07.
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Data for 2 are as follows. H NMR (CD2Cl2): 7.46−7.37 (m, 7H,
Ph), 7.25−7.14 (m, 18H, Ph), 6.95 (m, 2H, Ph/Ind), 6.69−6.57 (m,
10H, Ph), 6.40 (s, 1H, Ind), 5.82−5.75 (m, 2H, Ind), 5.51−5.42 (m,
2H, Ind). 31P{1H} NMR (CD2Cl2): 35.6 (s, PPh3). 11B NMR
(CD2Cl2): 0.1 (br s). 19F NMR (CD2Cl2): −132.55 (m, 2F, C6F4),
−133.67 (m, 4F, o-C6F5), −140.58 (m, 2F, C6F4), −161.15 (t, 2F, 3JFF
= 21 Hz, p-C6F5), −165.76 (m, 4F, m-C6F5), −192.04 (br s, 1F, BF).
13C{1H} NMR (partial, CD2Cl2): 133.75 (t, JPC = 5 Hz, Ph), 133.32 (s,
Ph), 132.83 (s, Ph), 131.53 (s, Ph), 131.21 (s, Ph), 130.47 (s, Ph),
130.18 (s, Ph), 130.17 (s, Ph), 129.21 (s, Ind), 128.82 (s, Ph), 128.43
(t, JPC = 5 Hz, Ph), 128.25 (s, Ph), 123.64 (s, Ind), 117.40 (s, Ph),
100.31 (s, Ind), 82.39 (s, Ind). Anal. Calcd for C71H42BF15P2Ru·
C6H12·1/2CH2Cl2 (1480.04): C, 62.87; H, 3.74. Found: C, 62.30; H,
4.13.
Synthesis of (indenyl)Ru(PPh3)2(CC(Ph)(CH(Ph)OB-
(C6F4H)3)) (6) and (indenyl)Ru(PPh3)2(CC(Ph)(CH(Ph)OAl-
(C6F5)3)) (7). These compounds were prepared in a similar fashion,
and thus only one preparation is detailed. B(C6F4H)3 (0.010 g, 0.021
mmol) in CH2Cl2 (0.3 mL) was added to 1 (0.017 g, 0.020 mmol) in
CH2Cl2 (0.3 mL). The reaction mixture was then added to PhCHO
(0.003 g, 0.028 mmol) and allowed to react for 2 h. The resulting red
solution was pumped dry and washed with pentane to yield a red solid
(0.019 g, 63%).
Synthesis of (indenyl)Ru(PPh3)2(CC(Ph)(C(O)OB-
(C6F4H)3)) (3). B(p-C6F4H)3 (0.014 g, 0.030 mmol) in CD2Cl2 (0.3
mL) was added to 1 (0.025 g, 0.030 mmol) in CD2Cl2 (0.3 mL). The
reaction mixture was then added to a J. Young tube, pressurized with
CO2, and allowed to react for 16 h. To the orange solution was added
cyclohexane (5 mL) by slow diffusion, yielding orange X-ray-quality
crystals of the final product (0.030 g, 74%).
1
Data for 6 are as follows. H NMR (CD2Cl2): 7.58−7.38 (m, 8H,
Ph), 7.33−7.23 (m, 4H, Ph), 7.23−6.61 (m, 19H, Ph), 6.58−6.43 (m,
4H, Ph), 6.27−6.18 (m, 3H, Ph), 6.11−5.95 (m, 5H, Ph), 5.53−5.46
(m, 3H, Ind), 5.32−5.23 (m, 2H, Ind), 5.03 (m, 2H, Ind), 4.45 (s, 1H,
1
Data for 3 are as follows. H NMR (CD2Cl2): 7.48−7.38 (m, 7H,
2
−CHO−). 31P{1H} NMR (CD2Cl2): 38.8 (d, JPP = 25 Hz, PPh3),
Ph), 7.21−7.00 (m, 17H, Ph), 6.79−6.65 (m, 14H, Ph), 6.56 (d, 2H,
JHH = 7 Hz, Ind), 6.22 (m, 1H, Ind), 5.62 (m, 2H, Ind), 5.45 (m, 2H,
Ind). 31P{1H} NMR (CD2Cl2): 37.4 (s, PPh3). 11B NMR (CD2Cl2):
−19.8 (s). 19F NMR (CD2Cl2): −133.16 (m, 6F, o-C6F4H), −142.97
(m, 6F, m-C6F4H). 13C{1H} NMR (partial, CD2Cl2): 165.08 (s, CO2),
134.08 (t, JPC = 5 Hz, Ph), 133.49 (t, JPC = 5 Hz, Ph), 133.44 (s, Ph),
133.11 (s, Ph), 132.85 (s, Ph), 132.63 (s, Ph), 131.29 (s, Ind), 130.85
(s, Ph), 130.47 (s, Ph), 129.99 (s, Ph), 128.62 (t, JPC = 6 Hz, Ph),
128.25 (s, Ph), 127.94 (s, Ph), 127.58 (s, Ph), 127.17 (s, Ph), 126.99
(s, Ph), 124.93 (s, Ph), 123.37 (s, Ind), 117.00 (s, Ph), 101.87 (s, Ph),
101.64 (s, Ph), 101.41 (s, Ph), 101.05 (s, Ph), 100.08 (s, Ind), 81.50
(s, Ind). IR (from KBr plate): ν 1638 cm−1 (CO). Anal. Calcd for
C72H45BF12P2Ru·1/2C6H12 (1386.03): C, 64.99; H, 3.71. Found: C,
64.88; H, 4.32.
33.7 (d, 2JPP = 25 Hz, PPh3). 11B NMR (CD2Cl2): −2.9 (s).19F NMR
(CD2Cl2): −131.05 (m, 6F, o-C6F5), −143.97 (m, 6F, m-C6F5).
13C{1H} NMR (partial, CD2Cl2) 135.02 (s, Ph), 134.49 (s, Ph),
133.87 (s, Ph), 133.05 (s, Ph), 131.60 (s, Ph), 131.13 (s, Ph), 130.77
(s, Ph), 129.81 (s, Ph), 128.97 (s, Ph), 128.70 (s, Ph), 128.35 (s, Ph),
128.29 (s, Ph), 127.87 (s, Ph), 127.50 (s, Ph), 127.11 (s, Ph), 126.16
(s, Ph), 125.97 (s, Ph), 125.57 (s, Ph), 125.27 (s, Ph), 124.84 (s, Ph),
123.67 (s, Ph), 123.27 (s, Ph), 122.80 (s, Ind), 116.09 (s, Ph), 109.17
(s, Ph), 98.91 (s, Ph), 94.96 (s, Ph), 83.39 (s, Ind), 79.10 (s, Ind),
79.38 (s, Ind), 74.47 (HSQC, CH−O). Anal. Calcd for
C78H51BF15OP2Ru (1406.05): C, 66.63; H, 3.66. Found: C, 67.07;
H, 3.81.
1
Data for 7 are as follows. Yield: 0.021 g, 63%. H NMR (C6D5Br):
7.37−6.69 (m, 34H, Ph), 6.48−6.34 (m, 6H, Ph/Ind), 5.49 (s, 2H,
Ind), 5.35 (m, 1H, Ind), 5.07 (m, 1H, −CHO−),. 31P{1H} NMR
(C6D5Br): 38.7 (d, 2JPP = 25 Hz, PPh3), 36.6 (d, 2JPP = 25 Hz, PPh3).
27Al NMR (C6D5Br): blank. 19F NMR (C6D5Br): −120.87 (m, 6F, o-
Synthesis of (indenyl)Ru(PPh3)2(CC(Ph)(C(O)OAl(C6F5)3))
(4). Al(C6F5)3tol (0.013 g, 0.021 mmol) in C6D5Br (0.3 mL) was
added to 1 (0.017 g, 0.020 mmol) in C6D5Br (0.3 mL). The reaction
mixture was then transferred to a J. Young tube, pressurized with CO2
,and allowed to react for 16 h at 75 °C. The orange solution was then
layered with cyclohexane (5 mL) and upon slow diffusion yielded
orange X-ray-quality crystals of the final product (0.021 g, 73%).
3
C6F5), −157.06 (t, 3F, JFF = 20 Hz, p-C6F5), −162.81 (m, 6F, m-
C6F5). 13C{1H} NMR (partial, C6D5Br): 145.60 (s, Ph), 137.50 (s,
Ph), 136.45 (s, Ph), 134.60 (m, Ph), 134.03 (m, Ph), 133.71 (m, Ph),
133.37 (m, Ph), 132.55 (s, Ph), 131.60 (s, Ph), 130.51−127.85 (m,
Ph), 127.37 (s, Ph), 127.28 (s, Ph), 126.97 (s, Ph), 126.69 (s, Ph),
125.38 (s, Ph), 124.96 (s, Ph), 123.61 (m, Ph), 123.21 (m, Ph), 121.10
(s, Ph), 117.01 (s, Ph), 116.08 (s, Ph), 100.85 (s, Ind), 133.90 (s, Ind),
126.01 (s, Ind), 81.24 (s, Ind), 79.58 (HSQC, CH−O). Anal. Calcd
for C78H48AlF15OP2Ru (1476.19): C, 63.46; H, 3.28. Found: C, 63.04;
H, 2.97.
1
Data for 4 are as follows. H NMR (C6D5Br): 7.10 (s, 3H, Ph),
7.05−6.94 (m, 6H, Ph), 6.86−6.76 (m, 13H, Ph), 6.74 (s, 3H, Ph),
6.72−6.66 (m, 2H, Ind), 6.54−6.38 (m, 10H, Ph), 5.83 (br s, 1H,
Ind), 5.26−5.18 (m, 2H, Ind), 4.98 (br s, 2H, Ind). 31P{1H} NMR
(C6D5Br): 36.9 (s, PPh3). 27Al NMR (C6D5Br): no signal observed.
3
19F NMR (C6D5Br): −121.79 (m, 6F, o-C6F5), −157.21 (t, 3F, JFF
=
20 Hz, p-C6F5), −163.36 (m, 6F, m-C6F5).13C{1H} NMR (partial,
C6D5Br): 166.85 (s, CO2), 134.02 (t, JPC = 6 Hz, Ph), 132.90 (s, Ph),
132.39 (s, Ph), 131.35 (s, Ph), 130.56 (s, Ph), 130.47 (s, Ph), 128.89
(s, Ph), 128.12 (t, JPC = 5 Hz, Ph), 127.93 (s, Ind), 127.47 (s, Ph),
127.19 (s, Ph), 124.56 (s, Ph), 123.21 (s, Ph), 122.63 (s, Ind), 122.00
(s, Ph), 116.84 (s, Ph), 100.34 (s, Ind), 81.24 (s, Ind). Anal. Calcd for
C72H42AlF15O2P2Ru (1414.08): C, 61.15; H, 2.99. Found: C, 60.78; H,
3.16.
Synthesis of (indenyl)Ru(PPh3)2(CC(Ph)C(Ph)CH(B-
(C6F4H)3)) (8) and (indenyl)Ru(PPh3)2(CC(Ph)C(Ph)CH(Al-
(C6F5)3)) (9). These compounds were prepared in a similar fashion,
and thus only one preparation is detailed. B(C6F4H)3 (0.019 g, 0.042
mmol) in CH2Cl2 (0.5 mL) was added to 1 (0.034 g, 0.040 mmol) in
CH2Cl2 (0.5 mL). Phenylacetylene (0.004 g, 0.040 mmol) was then
added to this reaction mixture, resulting in a deep red solution. This
solution was then layered with cyclohexane (5 mL) and upon slow
diffusion yielded red X-ray-quality crystals of the final product (0.050
g, 89%).
Synthesis of (indenyl)Ru(PPh3)2(CC(Ph)(C(OAl(C6F5)3)-
OAl(C6F5)3)) (5). Al(C6F5)3tol (0.026 g, 0.042 mmol) in C6D5Br
(0.3 mL) was added to 1 (0.017 g, 0.020 mmol) in C6D5Br (0.3 mL).
The reaction mixture was then added to a J. Young tube, pressurized
with CO2, and allowed to react for 16 h. The dark red solution was
then layered with cyclohexane (5 mL) and upon slow diffusion yielded
red X-ray-quality crystals of the final product (0.028 g, 75%).
1
Data for 8 are as follows. H NMR (CD2Cl2): 7.49 (br s, 1H,
CH), 7.43−7.36 (m, 6H, Ph), 7.27−7.11 (m, 13H, Ph), 7.09−7.01 (m,
2H, Ph/Ind), 6.91−6.78 (m, 4H, Ph), 6.76−6.54 (m, 18H, Ph), 6.40
(d, 2H, JHH = 7 Hz, Ph/Ind), 6.29 (s, 1H, Ph/Ind), 5.47−5.39 (m, 4H,
Ph/Ind). 31P{1H} NMR (CD2Cl2): 38.6 (s, PPh3). 11B NMR
(CD2Cl2): −15.1 (s). 19F NMR (CD2Cl2): −131.02 (m, 6F, o-
C6F4H), −144.64 (m, 6F, m-C6F4H). 13C{1H} NMR (partial,
1
Data for 5 are as follows. H NMR (C6D5Br): 7.13−6.64 (m, 23H,
Ph), 6.61−6.26 (m, 12H, Ph), 6.21 (t, 1H, JHH = 8 Hz, Ph), 5.96 (t,
2H, JHH = 8 Hz, Ind), 5.80 (d, 2H, JHH = 8 Hz, Ind), 5.13−5.02 (m,
E
dx.doi.org/10.1021/om401118n | Organometallics XXXX, XXX, XXX−XXX