3074 Organometallics, Vol. 22, No. 15, 2003
Umezawa-Vizzini and Lee
impurities in the solvents. Infrared (IR) spectra were recorded
on a Mattson Galaxy Serio FTIR 5000. Elemental analyses
were performed by Oneida Research.
H, C6H5CH2CH2P), 2.51 (m, 1 H, C6H5CH2CH2P), 2.35 (m, 1
H, C6H5CH2CH2P), 1.95 (d, J HH ) 6.3 Hz, 3 H, CH3CHCdCH),
1.91 (m, 5 H, Cy2), 1.80 (m, 6 H, Cy2) 1.27 (m, 11 H, Cy2). 13C
NMR (CD2Cl2; 75.5 MHz; 293 K): δ 162.38 (q, J CB ) 79.7 Hz),
Syn th esis of [(η6:η1-C6H5CH2CH2P Cy2)Ru CH3CO][B(3,5-
C6H3(CF 3)2)4] (3). A solution of 0.10 g (2.3 × 10-4 mol) of 1 in
CH2Cl2 (20 mL) was bubbled with CO at -76 °C for 3 min. To
this solution was added an aliquot of H+B- (0.21 g; 2.1 × 10-4
mol) in CH2Cl2 (5 mL) at -76 °C, and the solution was slowly
warmed to room temperature and stirred for 15 min. The
solution was concentrated to ∼5 mL under vacuum, and
hexanes were added to precipitate fine light yellow crystals.
The crystals were collected by filtration and dried under
vacuum. Yield: 0.067 g; 23%. 1H NMR (CD2Cl2; 300 MHz; 293
K): δ 7.72 (s, 8 H, B(3,5-C6H3(CF3)2)4), 7.56 (s, 4 H, B(3,5-C6H3-
(CF3)2)4), 6.39 (m, 2 H, η6-C6H5), 6.14 (d, J HH ) 6.3 Hz, 1 H,
η6-C6H5), 6.03 (m, 2 H, η6-C6H5), 2.96 (m, 1 H, C6H5CH2CH2P),
2.83 (m, 1 H, C6H5CH2CH2P), 2.59 (m, 2 H, C6H5CH2CH2P),
1.27-2.10 (m, 22 H, Cy2), 0.53 (d, J PH ) 3.0 Hz, 3 H, Ru-
CH3). 13C NMR (CD2Cl2; 75.5 MHz; 293 K): δ 198.01, 162.35
2
139.32, 135.44, 129.61, 129.34 (q, J CF ) 33.0 Hz), 125.24 (q,
1J CF ) 272.1 Hz), 118.13, 114.65, 111.66, 99.25, 94.43, 92.73
(d, J ) 7.2 Hz), 84.43, 84.17, 64.53, 52.53, 40.28, 37.72 (d, J CP
) 26 Hz), 35.43 (d, J CP ) 19.6 Hz), 34.50 (d, J ) 20.2 Hz),
31.58, 29.48, 28.98, 28.11, 27.98, 27.89, 27.73, 27.35, 27.23,
26.62, 20.11.
Syn t h esis of [(η6:η1-C6H 5CH 2CH 2P P h 2)R u (η3-CH3CH -
C5H5)][B(3,5-C6H3(CF 3)2)4] (6). This compound was prepared
using a procedure analogous to that used to prepare 5. Yield:
1
0.159 g; 52% of red crystals. H NMR (CD2Cl2; 300 MHz; 293
K): δ 7.25-7.74 (m, 22 H, PPh2, B(3,5-C6H3(CF3)2)4), 6.60 (m,
-CHdCH-), 6.26 (m, 1 H -CHdCH-), 6.12 (d, J HH ) 6.0 Hz,
1 H, η6-C6H5), 5.91, (d, J HH ) 6.0 Hz, 1 H, η6-C6H5), 5.81 (t,
J HH ) 6.0 Hz, 1 H, η6-C6H5), 5.28 (t, J HH ) 6.0 Hz, 1 H, η6-
C6H5), 4.20 (t, J HH ) 6.0 Hz, 1 H, η6-C6H5), 3.32 (m, 2 H, C6H5-
CH2CH2P), 3.05 (br s, 3 H, CCH2CH, η3-CH3CHCCH), 2.54
(m, 1 H, η3-CH3CHCCH), 2.43 (m, 2 H, C6H5CH2CH2P), 1.96
(d, J HH ) 6.0 Hz, 3 H, η3-CH3CHCCH). 13C NMR (CD2Cl2; 75.5
MHz; 293 K): δ 162.38 (q, J CB ) 79.7 Hz), 139.03, 134.73,
132.4-133.5 (m), 129.2 (m), 124.72 (q, 1J CF ) 272.6 Hz), 117.40,
114.91, 111.87, 101.81, 96.81 (d, J CP ) 2.1 Hz), 91.68 (d, J CP
) 9.7 Hz), 86.57, 85.48, 69.34, 58.65, 47.53 (d, J CP ) 33.4 Hz),
40.86, 28.26 (d, J CP ) 3.9 Hz), 20.45.
2
(q, J CB ) 79.7 Hz), 135.39, 134.76, 129.23 (q, J CF ) 25.1 Hz),
124.49 (q, 1J CF ) 272.7 Hz), 118.07, 110.96, 98.52, 97.87, 92.62,
92.41, 41.28 (d, J CP ) 29.4 Hz), 36.42 (d, J CP ) 27.3 Hz), 33.59
(d, J CP ) 23 Hz), 31.50, 26.1-28.9 (m), -22.01. IR (Nujol,
cm-1): 2017, 1278, 1126, 887, 839. Anal. Calcd for C54H46
RuPOBF24: C, 49.47; H, 3.51. Found: C, 49.21; H, 3.22.
-
Syn th esis of [(η6:η1-C6H5CH2CH2P P h 2)Ru CH3CO][B(3,5-
C6H3(CF 3)2)4] (4). A solution of 0.10 g (2.4 × 10-4 mol) of 2 in
CH2Cl2 (20 mL) was bubbled with CO at -76 °C for 3 min. To
this solution was added an aliquot of H+B- (0.21 g; 2.1 × 10-4
mol) in CH2Cl2 (5 mL) at -76 °C, and the solution was warmed
to room temperature and stirred for 15 min. The solution was
concentrated to ∼3 mL under vacuum, and hexanes were
added to precipitate an oily residue (crude yield 95%). The
hexanes were decanted, and ∼1 mL of CH2Cl2 was added to
the oily residue. After 1 week under an atmosphere of hexanes
vapor at 25 °C, light yellow crystals formed in the oily residue.
The crystals were carefully collected, washed with hexanes,
Syn th esis of th e Meta sta ble P r ecu r sor to 7: [(η6:η1-
C 6 H 5 C H 2 C H 2 P P h 2 )R u C H 3 (C H 2 dC H 2 )][B (3 ,5 -C 6 H 3 -
(CF 3)2)4]. A solution of 15 mg (3.6 × 10-5 mol) of 1 in CD2Cl2
(0.5 mL) was bubbled with ethylene at -76 °C for 3 min. To
this solution was added an aliquot of H+B- (32 mg; 3.2 × 10-5
mol) in CD2Cl2 (0.5 mL) at -76 °C, and the solution was
warmed to room temperature and stirred for 5 min. The
1
solvents were removed under vacuum. H NMR (CD2Cl2; 300
MHz; 293 K): δ 7.22-7.74 (m, 22 H, PPh2, B(3,5-C6H3(CF3)2)4),
6.35 (m, 2 H, η6-C6H5), 6.28 (t, J HH ) 5.7 Hz, 1 H, η6-C6H5),
5.78 (d, J HH ) 5.7 Hz, 1 H, η6-C6H5), 5.61 (t, J HH ) 5.7 Hz, 1
H, η6-C6H5), 3.40 (m, 2 H, CH2dCH2), 3.18 (m, 2 H, C6H5-
CH2CH2P), 2.69 (m, 2 H, C6H5CH2CH2P), 2.03 (m, 2 H, CH2d
CH2), -0.53 (d, J HP ) 7.8 Hz, 3 H, RuCH3).
1
and dried under vacuum. Yield: 0.020 g; 7%. H NMR (CD2-
Cl2; 300 MHz; 293 K): δ 7.60-7.80 (m, 20 H, PPh2, B(3,5-
C6H3(CF3)2)4), 7.26 (m, 2 H, PPh2), 6.62 (t, J HH ) 6.3 Hz, 1 H,
η6-C6H5), 6.56 (t, J HH ) 6.3 Hz, 1 H, η6-C6H5), 6.28, (d, J HH
)
6.3 Hz, 1 H, η6-C6H5), 6.22 (t, J HH ) 6.3 Hz, 1 H, η6-C6H5),
5.92 (d, J HH ) 6.3 Hz, 1 H, η6-C6H5), 3.61 (m, 1 H, C6H5-
CH2CH2P), 3.36 (m, 1 H, C6H5CH2CH2P), 2.90 (m, 1 H,
Syn t h esis of [(η6:η1-C6H 5CH 2CH 2P P h 2)R u Cl]2[B(3,5-
C6H3(CF 3)2)4]2 (7). A solution of 0.10 g (2.4 × 10-4 mol) of 2
in CH2Cl2 (20 mL) was bubbled with ethylene at -76 °C for
20 min. To this solution was added an aliquot of H+B- (0.21
g; 2.1 × 10-4 mol) in CH2Cl2 (5 mL) at -76 °C, and the solution
was warmed to room temperature and stirred for 1.5 h under
1.2 atm of ethylene. The volatiles were removed under vacuum,
and the resultant brownish yellow residue was washed with
hexanes and extracted with benzene. The benzene was evapo-
rated under vacuum. The crude product appeared to contain
predominantly [(η6:η1-C6H5CH2CH2PPh2)RuCH3(CH2dCH2)]-
[B(3,5-C6H3(CF3)2)4] with some uncharacterized Ru-H side
product, as judged by 1H NMR spectroscopy. This crude
product was dissolved in CH2Cl2 (20 mL), and the solution was
stirred for 2 days at room temperature. The reaction mixture
was concentrated to ∼3 mL under vacuum, and hexanes was
added to precipitate large red needles of 7. The crystals were
collected by filtration and dried under vacuum. Yield: 0.16 g;
C6H5CH2CH2P), 2.30 (m, 1 H, C6H5CH2CH2P), 0.29 (d, J HP
)
5 Hz, 3 H, RuCH3). 13C NMR (CD2Cl2; 75.5 MHz; 293 K): δ
196.03, 162.38 (q, J CB ) 79.7 Hz), 135.44, 131.7-134.1 (m),
1
128.4-130.4 (m), 125.23 (q, J CF ) 270.2 Hz), 118.09, 112.79,
102.47, 99.47, 93.20, 92.72, 48.94 (d, J CP ) 34.8 Hz), 30.35 (d,
J CP ) 15.4 Hz), -16.76. IR (Nujol, cm-1): 2004, 1276, 1124,
888, 842.
Syn t h esis of [(η6:η1-C6H 5CH 2CH 2P Cy2)R u (η3-CH3CH -
C5H5)][B(3,5-C6H3(CF 3)2)4] (5). A solution of 0.10 g (2.3 ×
10-4 mol) of 1 in CH2Cl2 (20 mL) was bubbled with acetylene
at -76 °C for 3 min. To this solution was added an aliquot of
H+B- (0.21 g; 2.1 × 10-4 mol) in CH2Cl2 (5 mL) at -76 °C,
and the solution was warmed to room temperature and stirred
for 90 min. The polyacetylene44 was collected by filtration. The
volatiles were removed from the filtrate under vacuum. The
resultant reddish brown residue was washed with hexanes and
extracted with benzene. The solution was filtered, and the
benzene was evaporated under vacuum. The product was
recrystallized from a mixture of CH2Cl2 and hexanes to afford
1
50%. H NMR (CD2Cl2; 300 MHz; 293 K): δ 7.07-7.95 (m, 22
H, PPh2, B(3,5-C6H3(CF3)2)4), 5.19 (t, 2 H, J HH ) 5.7 Hz, η6-
C6H5), 4.82 (t, J HH ) 5.7 Hz, 2 H, η6-C6H5), 4.65 (d, J HH ) 5.7
Hz, 1 H, η6-C6H5), 3.67 (m, 2 H, C6H5CH2CH2P), 2.48 (m, 2 H,
C6H5CH2CH2P). 13C NMR (CD2Cl2; 75.5 MHz; 293 K): δ 162.34
(q, J CB ) 79.7 Hz), 135.40, 133.4-134.7 (m), 127.9-130.0 (m),
124.51 (q, 1J CF ) 272.4 Hz), 119.01, 118.09, 95.44, 90.99, 77.07,
48.02 (d, J CP ) 34.0 Hz), 27.52. A satisfactory analysis was
not obtained, possibly due to contamination with the unchar-
acterized Ru-H side product described above. Anal. Calcd for
1
0.173 g (52% yield) of red crystals of 5. H NMR (CD2Cl2; 300
MHz; 293 K): δ 7.71 (s, 8 H, B(3,5-C6H3(CF3)2)4), 7.55 (s, 4 H,
B(3,5-C6H3(CF3)2)4), 6.60 (m, 1 H, -CHdCH-), 6.26 (m, 1 H,
-CHdCH-), 5.93 (d, J HH ) 5.7 Hz, 1 H, η6-C6H5), 5.79 (d, J HH
) 5.7 Hz, 1 H, η6-C6H5), 5.50 (t, J HH ) 5.7 Hz, 1 H, η6-C6H5),
5.12 (t, J HH ) 5.7 Hz, 1 H, η6-C6H5), 3.94 (t, J HH ) 5.7 Hz, 1
H, η6-C6H5), 3.86 (d, J HH ) 10.5 Hz, 1 H, η3-CH3CHCCH), 3.26
(m, 1 H, η3-CH3CHCCH), 3.02 (m, 2 H, CCH2CH), 2.69 (m, 2
C
104H102Ru2P2B2F48Cl2: C, 48.37; H, 3.95. Found: C, 45.94; H,
2.14.