Journal of the American Chemical Society
Page 6 of 9
1
outperforming it in styrene derivative reductions. Collec-
tively, these data also illustrate that the exceptional donor
abilities of [CBA] ligands provide a resource for catalyst
design that has seen limited use to date. Indeed we are
continuing to explore the utility of [CBA] ligands in catal-
ysis.
vacuum (121 mg, 93%). H NMR(CD2Cl2): 7.49 (d, 3JH-H=8.0
3
1
2
3
4
5
6
7
8
Hz, 4H, o-Ph), 7.42 (t, JH-H=8.0 Hz, 4H, m-Ph), 7.37-7.21
(m, 17H, PPh3& p-Ph), 7.01 (br s, 2H, m-OAr), 6.74 (br s,
2H, m-OAr), 6.44 (br s, 2H, p-OAr), 2.28 (br s, 6H,
2
OArCH3), 2.09 (br s, 6H, OArCH3), -24.21 (d, JH-P= 26.3
Hz, 1H, RuH). 13C NMR (CD2Cl2): 201.27 (CO), 151.02,
136.92 (d, 1JC-P= 36.4 Hz, ipso-PPh3), 134.96, 134.66 (d, 3JC-P
=
4
EXPERIMENTAL SECTION
11.3 Hz, o-PPh3), 129.84, 129.17 (d, JC-P= 10.0 Hz, m-PPh3),
5
127.67 (d, JC-P= 9.1 Hz, p-PPh3), 126.68, 125.93, 106.38 (d,
General Remarks: All manipulations were carried out
2JC-P= 83.2 Hz, CCBA), 17.48 (br, CH3). 31P NMR(CD2Cl2):
9
under an atmosphere of dry, O
2
-free N employing a Vac-
2
44.60 (d, JH-P = 23.5 Hz, PPh3). IR(KBr): 1892cm-1 (vCO).
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
uum Atmospheres glovebox or a Schlenk vacuum line.
Solvents were purified with a Grubbs-type column system
manufactured by Innovative Technology and dispensed
into thick-walled Straus flasks equipped with Teflon-valve
stopcocks. Deuterated dichloromethane was distilled un-
der reduced pressure from [CaH2] and degassed by suc-
cessive freeze-pump-thaw cycles. Deuterated benzene
Anal. Calcd. for C50H44ClN2O3PRu (888.39): C, 67.60; H,
4.99; N, 3.15. Found: C, 67.87; H, 5.34; N, 2.93.
Synthesis of [Ru(CBA)(SIMes)(CO)HCl] (3): To a solu-
tion of 1 (150 mg, 0.130 mmol) in THF (5 mL) was added
[SIMes] (140 mg, 0.457 mmol) and the solution was re-
fluxed for 24 hours. The solution was cooled to room
temperature and concentrated to approximately 1 mL.
Pentane (15 mL) was added to precipitate the product as a
bright yellow-orange solid, which was washed with pen-
tane (3 x 10 mL) and dried under high vacuum (111 mg,
1
was distilled from purple sodium benzophenone ketyl. H
and 13C NMR spectra were recorded at 25°C on Bruker 400
MHz spectrometers, unless otherwise noted. Chemical
shifts are reported in parts per million are given relative
to [SiMe4] and referenced to the residual solvent signal.
Combustion analyses were performed in house employing
a Perkin-Elmer CHN Analyzer. IR spectra were collected
on a Perkin-Elmer Spectrum One FT-IR instrument. Cy-
clic bent allene [(C6H3Me2O)2C3(NPh)2] was prepared ac-
cording to literature procedures24,56. [RuHCl(CO)(PPh3)3]
and [Me3SiOSO2CF3] were purchased from Strem and
used without subsequent purification. All commercially
available substrates were purchased from Aldrich or Acros
and were degassed prior to catalysis, but were not dried
or further purified. Nitrile Butadiene rubber was provided
by Lanxess. O-Methylated terpinen-4-ol was synthesized
according to literature procedures86
1
92%). H NMR(C6D6): 6.88 (br s, 2H, Mes), 6.86-6.77 (m,
6H), 6.75 (d, JH-H= 8.0 Hz, 4H, m-OAr), 6.65 (br s, 2H,
3
Mes), 6.60-6.57 (m, 6H), 3.30 (m, 4H, NCH2CH2N), 2.73
(br s, MesCH3, 6H), 2.51 (br s, MesCH3, 6H), 2.15 (br s,
OArCH3, 12H), 2.05 (br s, MesCH3, 6H), -26.04 (s, 1H, Ru-
H). 13C NMR (CD2Cl2): 221.40 (NCN), 203.37 (CO), 171.39
(NCO), 152.38, 137.71, 137.64, 137.11, 136.81, 134.91, 130.38,
129.33, 129.30, 129.18, 128.93, 128.76(br), 127.71, 125.39,
114.08 (CCBA), 51.18 (NCCN), 20.96 (MesCH3), 19.20
(MesCH3), 19.15 (MesCH3), 16.76 (br, XylCH3). IR(KBr):
1881cm-1 (vCO). Anal. Calcd. for C53H55ClN4O3Ru (932.55):
C, 68.26; H, 5.94; N, 6.01. Found: C, 68.22; H, 5.38; N, 5.83.
Synthesis of [Ru(CBA)(PPh3)(CO)H(OSO2CF3)] (4):
Employing silylated glassware, compound 2 (50 mg,
0.056 mmol) was dissolved in THF (2 mL) and
[Me3SiOSO2CF3] (10.5 μL, 0.058 mmol) was added. Solvent
was removed under high vacuum and yellow solid was
washed with pentane (3 x 5 mL) and dried under high
vacuum (54 mg, 96%). Small amounts (~5 mol%) of in-
separable [CBAH][OTf] are also observed due to minor
acid impurities in Me3SiOSO2CF3.1H NMR(CD2Cl2): 7.53
Synthesis of [Ru(CBA)(PPh3)2(CO)HCl] (1): Cyclic bent
allene (271 mg, 0.588 mmol) was added to a suspension of
[Ru(PPh3)3(CO)HCl] (504 mg, 0.529 mmol) in toluene (10
mL) and the mixture was stirred overnight (16 hrs). The
suspension was then filtered through a plug of celite and
the solvent was removed under vacuum without stirring,
causing X-ray quality crystals of the product to precipitate
in a red-brown oil. The mixture was triturated with small
successive portions of diethyl ether until the supernatant
became yellow in color. The crystalline beige solid ob-
tained was further washed with pentane (2 x 5mL) and
dried under high vacuum (289 mg, 47%). No NMR data
could be obtained as the complex readily dissociates tri-
phenylphosphine in solution, forming compound 2.
3
(d, JH-H=8.0 Hz, 4H, o-Ph), 7.45-7.31 (m, 15H, o-PPh3, p-
3
PPh3, m-Ph & p-Ph), 7.23 (t, JH-H=8.0 Hz, 6H, m-PPh3),
7.01 (br s, 2H, m-OAr), 6.78 (br s, 2H, m-OAr), 6.09 (br s,
2H, p-OAr), 2.41 (br s, 6H, OArCH3), 2.14 (br s, 6H,
2
OArCH3), -23.38 (d, JH-P= 23.3 Hz, 1H, RuH). 13C NMR
2
IR(KBr):
1899cm-1
(vCO).
Anal.
Calcd.
for
(CD2Cl2): 204.37 (d, JC-P= 15.3 Hz, CO), 158.77, 150.38,
135.39 (d, 1JC-P= 37.3 Hz, ipso-PPh3), 134.19 (d, 3JC-P= 11.7 Hz,
C50H44ClN2O3PRu (1150.67): C, 70.98; H, 5.17; N, 2.43.
Found: C, 71.24; H, 5.15; N, 2.45.
o-PPh3), 133.80 (br), 130.06, 129.99, 129.80, 129.62 (d, 5JC-P
=
5
1.9 Hz, p-PPh3), 129.02, 128.17 (br), 128.11 (d, JC-P= 9.0 Hz,
1
m-PPh3), 103.05 (d, JC-P= 77.5Hz, CCBA), 17.25 (br, Me). 19F
Synthesis of [Ru(CBA)(PPh3)(CO)HCl] (2): To a solu-
tion of 1 (168 mg, 0.146 mmol) in THF (5 mL) was added
[BH3] (1.0 M in THF, 146 μL, 0.146 mmol). The solution
was concentrated to approximately 1 mL and pentane (15
mL) was added to precipitate the product. The bright yel-
low solid was collected by filtration and dried under high
NMR(CD2Cl2): -78.68 (s) (OSO2CF3). 31P NMR(CD2Cl2):
2
43.16 (d, JH-P = 23.5 Hz, PPh3). IR(KBr): 1919 cm-1 (vCO).
Anal. Calcd. for C54H55F3ClN4O6PRuS (1002.01) C, 61.13; H,
4.43; N, 2.80. Found: C, 61.23; H, 4.84; N, 2.72.
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