G. Albertin, S. Antoniutti, A. Bacchi, G. Pelizzi, G. Zanardo
FULL PAPER
was removed under reduced pressure to leave an oil, which was
triturated with ethanol (2 mL) containing an excess amount of
NaBPh4 (0.46 mmol, 157 mg). An orange solid slowly separated
out, which was filtered and crystallised from ethanol. Yield: 248 mg
0.15 mmol) in 1,2-dichloroethane was added an excess amount of
phenylacetylene (0.6 mmol, 67 µL), and the reaction mixture was
heated at reflux for 1 h. The solvent was removed under reduced
pressure to give an oil, which was triturated with ethanol (3 mL)
containing an excess amount of NaBPh4 (0.30 mmol, 103 mg). A
yellow solid slowly separated out by cooling the resulting solution
for 2a+3a (78%), 225 mg for 2b+3b (74%). Data for 2a+3a: ΛM
=
51.6 Scm2 mol–1. 1H NMR (300 MHz, CD2Cl2, 20 °C): δ = 7.60–
6.87 (m, 30 H, Ph), 6.50 and 5.65 (AB2CXY, X = α-H, Y = β-H; to –25 °C, which was filtered and crystallised from ethanol. Yield:
JA,X = 16.2 Hz, JA,Y = 8.9 Hz, JB,X = 3.5 Hz, JB,Y = 3.1 Hz, JC,X
128 mg (66%). ΛM = 55.1 Scm2 mol–1. 1H NMR (300 MHz,
= 0.5 Hz, JC,Y = 0.3 Hz, JX,Y = 0.1 Hz; 2 H; CH2 vinyl; 2a), 8.28 CD2Cl2, 20 °C): δ = 8.05–6.85 (m, 30 H, Ph), 4.30, 3.85 (m, 24 H,
and 6.75 (AB2CXY, X = α-H, Y = β-H; JA,X = 5.35 Hz, JA,Y
=
CH2 phos), 1.40, 1.30, 1.03 (t, J = 7.0 Hz, 36 H, CH3 phos) ppm.
31P{1H} NMR (121.52 MHz, CD2Cl2, 20 °C): δ = 137.9, 136.3 and
121.5 (ABC2, JA,B = 49.3 Hz, JA,C = 58.0 Hz, JB,C = 63.8 Hz) ppm.
C64H91BO12P4Ru (1288.18): calcd. C 59.67, H 7.12; found C 59.48,
10.3 Hz, JB,X = 2.0 Hz, JB,Y = 3.3 Hz, JC,X = 2.0 Hz, JC,Y = 1.0 Hz,
JX,Y = 10.5 H; 2 H; CH2 vinyl; 3a), 4.51, 4.43 (m, 1 H, OH), 4.01–
3.58 (m, 24 H, CH2 phos), 1.35, 1.32, 1.27, 1.25, 1.16, 1.14 (t, J =
7.0 Hz, 36 H, CH3 phos) ppm. 31P{1H} NMR (121.52 MHz, H 7.26.
CD2Cl2, 20 °C): δ = 104.5, 93.0 and 76.5 (AB2C, JA,B = 39.7 Hz,
[Os{η3-p-tolyl-C3C(H)-p-tolyl}{P(OEt)3}4]BPh4 (6): To a solution
JA,C = 25.0 Hz, JB,C = 46.9 Hz, 2a), 106.1, 95.3 and 79.4 (AB2C,
JA,B = 40.0 Hz, JA,C = 26.6 Hz, JB,C = 46.9 Hz, 3a) ppm. 13C NMR
(75.48 MHz, CD2Cl2, 20 °C): δ = 165–122 (m, Ph); 145.1 (m, C2),
119.7 (m, C1), 114.4 (s, C3), 61.6 (m, CH2 phos), 16.2 (m, CH3
phos) (2a); 145.8 (m, C2), 133.8 (m, C1), 101.4 (s, C3), 62.6 (m,
CH2 phos), 16.5 (m, CH3 phos) (3a) ppm.C63H93BO13OsP4
(1383.32): calcd. C 54.70, H 6.78; found C 54.58, H 6.90. Data for
2b+3b: ΛM = 53.0 Scm2 mol–1. 1H NMR (300 MHz, CD2Cl2,
20 °C): δ = 7.65–6.86 (m, 25 H, Ph), 5.56 and 6.05 (ABCDXY, X
= α-H, Y = β-H; JA,X = 8.18 Hz, JA,Y = 16.20 Hz, JB,X = 2.64 Hz,
JB,Y = 3.76 Hz, JC,X = 2.64 Hz, JC,Y = 3.76 Hz, JD,X = 2.74 Hz,
JD,Y = 1.8 Hz, JX,Y = 0.22 Hz; 2 H; CH2 vinyl; 2b), 6.27 and 8.05
(ABCDXY, X = α-H, Y = β-H; JA,X = 10.90 Hz, JA,Y = 2.6 Hz,
of [Os{η2-C=(CH2)CPh2OH}{P(OEt)3}4]BPh4 (2a+3a; 208 mg,
0.15 mmol) in 1,2-dichloroethane (10 mL) was added an excess
amount of p-tolyl acetylene (0.6 mmol, 78 µL), and the reaction
mixture was heated at reflux for 2 h. The solvent was removed un-
der reduced pressure to give an oil, which was triturated with etha-
nol (3 mL) containing an excess amount of NaBPh4 (0.30 mmol,
103 mg). A yellow solid slowly separated out by cooling the re-
sulting solution to –25 °C, which was filtered and crystallised from
ethanol. Yield: 38 mg (18%). ΛM = 55.0 Scm2 mol–1. 1H NMR
(300 MHz, CD2Cl2, 20 °C): δ = 7.85–6.86 (m, 28 H, Ph), 4.20–4.00,
3.80–3.60 (m, 24 H, CH2 phos), 2.40, 2.35 (s, 6 H, CH3 p-tolyl),
1.39, 1.28, 1.01 (t, J = 7.0 Hz, 36 H, CH3 phos) ppm. 31P{1H}
NMR (121.52 MHz, CD2Cl2, 20 °C): δ = 93.6, 83.4 and 83.0
(ABC2, JA,B = 24.3 Hz, JA,C = 38.8 Hz, JB,C = 37.5 Hz) ppm. 13C
NMR (75.48 MHz, CD2Cl2, 20 °C): δ = 165–122 (m, Ph), 141.3
JB,X = 3.9 Hz, JB,Y = 2.0 Hz, JC,X = 3.9 Hz, JC,Y = 2.0 Hz, JD,X
=
0.96 Hz, JD,Y = 0.42 Hz, JX,Y = 11.3 Hz; 2 H; CH2 vinyl; 3b), 4.16–
3.45 (m, 24 H, CH2 phos), 4.05, 3.80 (m, 1 H, OH), 1.65, 1.64 (s,
3 H, CH3-C3), 1.36, 1.34, 1.28, 1.26, 1.08 (t, J = 7.0 Hz, 36 H,
CH3 phos) ppm. 31P{1H} NMR (121.52 MHz, CD2Cl2, 20 °C): δ
1
(dm, JC,H = 160 Hz, C-δ], 111.3 (m, C-α or C-β), 62.2 (m, CH2
phos), 22.0, 21.7 (s, CH3 p-tolyl), 16.1 (m, CH3 phos) ppm.
C66H95BO12OsP4 (1405.37): calcd. C 56.41, H 6.81; found C 56.50,
H 6.74.
= 103.7, 96.2, 95.9 and76.9 (ABCD, JA,B = 38.9 Hz, JA,C
38.9 Hz, JA,D = 26.6 Hz, JB,C = 1.30 Hz, JB,D = 46.3 Hz, JC,D
=
=
46.3 Hz, 2b), 105.8, 97.7, 96.6 and 80.1 (ABCD, JA,B = 38.5 Hz,
JA,C = 38.5 Hz, JA,D = 27.4 Hz, JB,C = 1.60 Hz, JB,D = 45.8 Hz,
JC,D = 45.8 Hz, 3b) ppm. 13C NMR (75.48 MHz, CD2Cl2, 20 °C):
δ = 165–122 (m, Ph); 148.1 (dm, C2), 117.7 (m, C1), 114.4 (s, C3),
62.5 (m, CH2 phos), 34.8 (s, CH3-C3), 16.2 (m, CH3 phos) (2b);
165–122 (m, Ph), 142.3 (dm, C1), 134.63 (t, C2), 92.65 (d, C3), 61.4
(m, CH2 phos), 29.9 (s, CH3-C3), 16.4 (m, CH3 phos) (3b) ppm.
C58H91BO13OsP4 (1321.25): calcd. C 52.73, H 6.94; found C 52.87,
H 7.05.
[Os(C=C=C=Ph2){P(OEt)3}5](BPh4)2 (7a): An equimolar amount
of CH3OTf (0.35 mmol, 39 µL) was added to a solution of the hy-
dride OsH2[P(OEt)3]4 (0.35 mmol, 300 mg) in toluene (8 mL) al-
lowed to stand under an argon atmosphere and cooled to –196 °C.
The reaction mixture was warmed to room temperature, stirred for
30 min and cooled again to –196 °C. An equimolar amount of
triflic acid (TfOH, 0.35 mmol, 31 µL) was added, and the reaction
mixture was brought to room temperature and stirred for 1 h. After
cooling to –196 °C, an excess amount of 1,1-diphenyl-2-propyn-1-
ol (1.05 mmol, 219 mg) in CH2Cl2 (8 mL) was added, and the solu-
tion, brought to room temperature, was stirred for 8 h. The solvent
was removed under reduced pressure to give an oil, which was tritu-
rated with ethanol (2 mL) containing an excess amount of NaBPh4
(1 mmol, 0.34 g). A purple solid slowly separated out, which was
filtered and crystallised from CH2Cl2 and ethanol. Yield: 142 mg
[Ru(PhNHNH2)2{P(OEt)3}4](BPh4)2 (4): An excess amount of
phenylhydrazine (0.92 mmol, 90 µL) was added to a solution of
[Ru{η2-C(=CH2)CPh2OH}{P(OEt)3}4]BPh4 (300 mg, 0.23 mmol)
in 1,2-dichloroethane (15 mL), and the reaction mixture was heated
at reflux for 1 h. The solvent was removed under reduced pressure
to give an oil, which was treated with ethanol (5 cm3) containing
an excess amount of NaBPh4 (0.46 mmol, 157 mg). A yellow solid
slowly separated out from the resulting solution, which was filtered
and crystallised from CH2Cl2 and ethanol. Yield: 168 mg (45%).
(22%). ΛM = 124 Scm2 mol–1. IR (KBr): ν = 1955 [m (νC=C=C)]
˜
1
cm–1. H NMR (300 MHz, CD2Cl2, 20 °C): δ = 7.60–6.85 (m, 50
H, Ph), 4.10 (m, 30 H, CH2 phos), 1.35, 1.32 (t, J = 7.0 Hz, 45 H,
CH3 phos) ppm. 31P{1H} NMR (121.52 MHz, CD2Cl2, 20 °C): δ
= 85.1 and 69.1 (A4B, JA,B = 40.7 Hz) ppm. 13C NMR (75.48 MHz,
CD2Cl2, 20 °C): δ = 281.5 (br. m, C-α), 195.5 (br. m, C-β), 165–
120 (m, Ph), 162.9 (s, C-γ), 62.9, 62.5 (d, CH2 phos), 16.2 (m, CH3
phos) ppm. C93H125B2O15OsP5 (1849.69): calcd. C 60.39, H 6.81;
found C 60.21, H 6.90.
ΛM = 122 Scm2 mol–1. IR (KBr): ν = 3318 (m), 3300 (w), 3240 [w,
˜
(νNH)], 1605 [w, (δNH )] cm–1. 1H NMR [300 MHz, (CD3)2CO,
2
20 °C]: δ = 7.48–6.67 (m, 50 H, Ph), 6.61 (br. t, 2 H, NH), 5.80
(br., 4 H, NH2), 4.55–4.30 (m, 24 H, CH2), 1.42, 1.39 (t, J = 7.0 Hz,
36 H, CH3) ppm. 31P{1H} NMR [121.52 MHz, (CD3)2CO, 20 °C]:
δ = 130.3 and 120.4 (A2B2, JA,B = 62.0 Hz) ppm. C84H116B2N4O12-
P4Ru (1620.45): calcd. C 62.26, H 7.22, N 3.46; found C 62.04, H
7.30, N 3.33.
X-ray Crystallography: Mo-Kα radiation (λ = 0.71073 Å), T = 293K
with a SMART AXS 1000 CCD diffractometer. Lorentz, polariza-
tion and absorption corrections were applied.[27] Structure was
solved by direct methods by using SIR97[28] and refined by full-
[Ru{η3-PhC3C(H)Ph}{P(OEt)3}4]BPh4 (5a): To
[Ru{η2-C=(CH2)CPh2OH}{P(OEt)3}4]BPh4
(1a)
a
solution of
(200 mg,
1918
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Eur. J. Inorg. Chem. 2008, 1913–1920