Journal of the American Chemical Society
ARTICLE
(Cy-PSiP)RuNH(2,6-Me2C6H3) (5). A slurry of LiNH(2,6-
Me2C6H3) (0.017 g, 0.14 mmol) in ca. 3 mL of benzene was added to
a slurry of 1 (0.10 g, 0.07 mmol) in ca. 5 mL of benzene at room tem-
perature. The reaction mixture was stirred for 1 h at room temperature
over which time a color change from orange to dark red was observed
along with the formation of a white precipitate. The solution was then
filtered through Celite, and the filtrate solution was retained. The volatile
components of the filtrate solution were removed in vacuo, and the
resulting residue was triturated with pentane (ca. 1 mL) to yield 5
(0.11 g, 96%) as a dark red solid. 1H NMR (500 MHz, benzene-d6): δ
7.92 (d, 2 H, Harom, J = 7 Hz), 7.57 (br s, 1 H, NH), 7.49 (m, 2 H, Harom),
7.24ꢀ7.18 (overlapping resonances, 4 H, Harom + 2,6-Me2C6H3), 7.05
(t, 2 H, Harom, J = 7 Hz), 6.86 (t, 1 H, 2,6-Me2C6H3, J = 7 Hz), 2.52 (m, 2
H, PCy), 2.31 (s, 6 H, 2,6-Me2C6H3), 2.21 (m, 2 H, PCy), 1.83 (m, 4 H,
PCy), 1.65ꢀ0.70 (overlapping resonances, 37 H, PCy + SiMe; a singlet
resonance at 1.25 ppm was assigned to the SiMe protons by use of a
1.92 (br s, 2 H, PCy), 1.85ꢀ0.93 (br overlapping resonances, 37 H,
PCy), 0.89 (s, 3 H, SiMe), 0.62 (br s, 2 H, PCy). 13C{1H} NMR (125.8
MHz, benzene-d6): δ 169.9 (Ru-η5-C6H5O), 158.7 (d, Carom, J = 44
Hz), 147.2 (d, Carom, J = 45 Hz), 132.2 (d, CHarom, J = 19 Hz), 129.8
(CHarom), 129.0 (CHarom), 126.9 (CHarom), 99.1 (Ru-η5-C6H5O), 83.3
(Ru-η5-C6H5O), 67.6 (Ru-η5-C6H5O), 41.4 (br, CHCy), 38.9 (br,
CHCy), 32.4ꢀ25.9 (br, CH2Cy), 2.7 (SiMe). 31P{1H} NMR (300 K,
202.5 MHz, benzene-d6): δ 74.7 (br m). 31P{1H} NMR (363 K, 202.5
MHz, toluene-d8): δ 71.5 (s). 31P{1H} NMR (213 K, 101.3 MHz,
toluene-d8): δ 87.7 (br s, 1 P, Cy-PSiP), 66.7 (br s, 1 P, Cy-PSiP). 29Si
NMR (99.4 MHz, benzene-d6): δ 57.4. Anal. Calcd for C43H60OP2-
SiRu: C, 65.87; H, 7.71. Found: C, 65.85; H, 7.90. A single crystal of
7 C6H6 suitable for X-ray diffraction analysis was grown from a
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concentrated benzene solution.
(Cy-PSiP)RuH(η2:η2-H2BNH2) (8). A solution of H3B NH3 (0.004 g,
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0.12 mmol) in ca. 2 mL of benzene was added to a room-temperature
solution of 2 (0.092 g, 0.12 mmol) in ca. 10 mL of benzene. An immediate
color change from red to yellow was observed. The volatile components of
the reaction mixture were removed in vacuo, and the remaining solid was
triturated with hexanes (2 ꢁ 1mL) toyield8(0.070 g, 81%) as a yellow solid.
1H NMR (500 MHz, benzene-d6): δ 8.25 (d, 2 H, Harom, J = 7 Hz), 7.51
(m, 2 H, Harom), 7.30 (t, 2 H, Harom, J = 7 Hz), 7.20 (t, 2 H, Harom, J = 7 Hz),
2.44 (br s, 2 H, NH2), 2.36 (m, 4 H, PCy), 1.94ꢀ1.17 (overlapping
resonances, 40 H, PCy), 0.99 (s, 3 H, SiMe), ꢀ3.36 (br s, 1 H, RuHB),
ꢀ7.50 (br s, 1 H, RuHB), ꢀ12.62 (t, 1 H, RuH, 2JHP = 26 Hz). 13C{1H}
NMR (125.8 MHz, benzene-d6): δ 161.6 (apparent t, Carom, J = 26 Hz),
146.1 (apparent t, Carom, J = 24 Hz), 133.1 (apparent t, CHarom, J = 10 Hz),
129.2 (CHarom), 129.1 (CHarom), 126.8 (CHarom), 42.1 (apparent t, CHCy,
J = 8 Hz), 35.5 (apparent t, CHCy, J = 13 Hz), 31.0 (CH2Cy), 30.4 (CH2Cy),
30.0 (CH2Cy), 29.0 (CH2Cy), 28.5ꢀ27.7 (overlapping resonances, CH2Cy),
9.7 (SiMe). 31P{1H} NMR (202.5 MHz, benzene-d6): δ 90.1. 29Si NMR
(99.4 MHz, benzene-d6): δ 63.5. 11B{1H} NMR (160 MHz, benzene-d6): δ
44.1 (br). 15N NMR (50.7 MHz, benzene-d6): δ ꢀ310.1. IR (Nujol, cmꢀ1):
ν 3499, 3399 (s, NꢀHs,as); 1964 (m br, RuꢀH); 1818 (w br, RuꢀHꢀB);
1588 (s, NꢀHbend). Anal. Calcd for C37H60P2NBSiRu: C, 61.65; H, 8.39; N,
1.94. Found: C, 61.31; H, 8.36; N, 1.69. A single crystal of 8 suitable for X-ray
diffraction analysis was grown from a concentrated Et2O solution at ꢀ35 °C.
(Cy-PSiP)RuH(η2:η2-H2BNMe2) (9). A solution of of 2 (0.074 g,
0.097 mmol) in ca. 5 mL of benzene was treated with a solution of
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1Hꢀ C HSQC experiment), 0.62 (br m, 2 H, PCy). 13C{1H} NMR
(125.8 MHz, benzene-d6): δ 158.4 (Carom), 158.3 (Me2C6H3, Cipso),
148.1 (Carom), 131.2 (d, CHarom, J = 19 Hz), 128.3 (CHarom), 127.7 (2,6-
Me2C6H3, CHmeta), 126.6 (d, CHarom, J = 5 Hz), 125.8 (CHarom), 122.9
(NCipso), 116.2 (2,6-Me2C6H3, CHpara), 39.7 (d, CHCy, J = 13 Hz), 38.0
(d, CHCy, J = 25 Hz), 32.9 (CH2Cy), 29.7 (CH2Cy), 28.6ꢀ26.8
(overlapping resonances, CH2Cy), 26.5 (CH2Cy), 26.1 (CH2Cy), 18.8
(Me2C6H3), ꢀ1.7 (SiMe). 31P{1H} NMR (202.5 MHz, benzene-d6): δ
94.2. 29Si NMR (99.4 MHz, benzene-d6): δ 57.2. 15N NMR (50.7 MHz,
benzene-d6): δ ꢀ219.1. Anal. Calcd for C45H65P2NSiRu: C, 66.63; H,
8.13; N, 1.76. Found: C, 66.50; H, 7.81; N, 1.68. A single crystal of 5
suitable for X-ray diffraction analysis was grown from a concentrated
diethyl ether solution at ꢀ30 °C.
[(Cy-PSiP)RuOH]2 (6). A solution of 2 (0.21 g, 0.28 mmol) in ca.
3 mL of benzene was treated with degassed H2O (0.005 mL, 0.28
mmol). An immediate color change from red to orange was observed.
The volatile components of the reaction mixture were removed in vacuo,
and the solid was triturated with pentane (2 ꢁ 1 mL) to yield 6 (0.19 g,
94%) as an orange solid. 1H NMR (500 MHz, benzene-d6): δ 8.02 (br s,
1 H, Harom), 7.72 (br s, 1 H, Harom), 7.72 (br s, 1 H, Harom), 7.51 (br s,
1 H, Harom), 7.24 (br s, 2 H, Harom), 7.04 (br s, 2 H, Harom), 6.94 (br s,
1 H, Harom), 3.22 (br s, 1 H, PCy), 3.03 (br s, 1 H, PCy), 2.79 (br s, 1 H,
PCy), 2.64 (br s, 1 H, PCy), 2.51 (br s, 1 H, PCy), 2.42 (br s, 1 H, PCy),
2.24 (m, 2 H, PCy), 2.09ꢀ0.80 (overlapping resonances, 34 H, PCy +
SiMe; a singlet resonance at 1.52 ppm was assigned to the SiMe protons
H3B NHMe2 (0.006 g, 0.097 mmol) in ca. 2 mL of benzene at room
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temperature. An immediate color change from red to yellow was ob-
served. The volatile components of the reaction mixture were removed
in vacuo, and the remaining solid was washed with pentane (2 ꢁ 1 mL)
to yield 9 (0.049 g, 67%) as a white solid. 1H NMR (300 K, 500 MHz,
benzene-d6): δ 8.26 (d, 2 H, Harom, J = 7 Hz), 7.53 (m, 2 H, Harom), 7.31
(apparent t, 2 H, Harom, J = 7 Hz), 7.20 (apparent t, 2 H, Harom, J = 7 Hz),
2.59 (s, 6 H, NMe2), 2.45ꢀ2.30 (overlapping resonances, 4 H, PCy),
1.96ꢀ1.04 (overlapping resonances, 40 H, PCy), 0.97 (s, 3 H, SiMe),
ꢀ3.29 (br s, 1 H, H2B), ꢀ7.49 (br s, 1 H, H2B), ꢀ13.07 (t, 1 H, RuH,
2JHP = 25 Hz). 13C{1H} NMR (300 K, 125.8 MHz, benzene-d6): δ 161.7
(apparent t, Carom, JCP = 26 Hz), 146.2 (apparent t, Carom, JCP = 24 Hz),
133.0 (apparent t, CHarom, J = 10 Hz), 129.1 (CHarom), 129.0 (CHarom),
126.8 (CHarom), 42.7 (apparent t, CHCy, J = 8 Hz), 40.9 (br s, NMe2),
35.5 (apparent t, CHCy, J = 13 Hz), 31.3 (CH2Cy), 30.4 (CH2Cy), 30.1
(CH2Cy), 29.1 (CH2Cy), 28.4 (m, CH2Cy), 28.1 (m, CH2Cy), 27.9ꢀ27.7
(overlapping resonances, CH2Cy), 27.2 (CH2Cy), 10.5 (SiMe). 31P{1H}
NMR (300 K, 202.5 MHz, benzene-d6): δ 91.2. 29Si NMR (300 K, 99.4
MHz, benzene-d6): δ 63.7. 11B NMR (300 K, 160 MHz, benzene-d6): δ
43.9 (br). IR (thin film, cmꢀ1): ν 1966 (m br, RuꢀH); the BꢀH
stretches could not be unequivocally identified. Anal. Calcd for
C39H64P2NBSiRu: C, 62.55; H, 8.61; N, 1.87. Found: C, 62.34; H,
8.98; N, 1.68. A single crystal of 9 suitable for X-ray diffraction analysis
was grown from a concentrated Et2O solution at ꢀ35 °C.
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by use of a 1Hꢀ C HSQC experiment), 0.65 (br m, 2 H, PCy), 0.37
(br s, 1 H, PCy), ꢀ0.13 (br s, 1 H, PCy), ꢀ0.37 (br s, 1 H, PCy), ꢀ0.74
(s, 1 H, OH). 13C{1H} NMR (125.8 MHz, benzene-d6): δ 160.4 (br,
Carom), 132.7 (m, CHarom), 131.1 (m, CHarom), 129.2 (CHarom), 128.9
(CHarom), 127.8 (CHarom), 126.4 (CHarom), 126.3 (CHarom), 41.3 (m,
CHCy), 39.9 (m, CHCy), 36.1 (m, CHCy), 34.8ꢀ26.7 (br overlapping
resonances, CH2Cy), 3.7 (SiMe). 31P{1H} NMR (300 K, 202.5 MHz,
benzene-d6): δ 91.2 (d, 2 P, 2JPP = 25 Hz), 86.5 (d, 2 P, 2JPP = 25 Hz).
31P{1H} NMR (363 K, 202.5 MHz, toluene-d8): δ 94.8 (br s). 29Si NMR
(99.4 MHz, benzene-d6): δ 68.7. Anal. Calcd for C74H112P4O2Si2Ru2:
C, 62.77; H, 7.97. Found: C, 62.34; H, 8.15. A single crystal of 6 C7H8
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suitable for X-ray diffraction analysis was grown from a concentrated
toluene solution.
(Cy-PSiP)Ru(η5-C6H5O) (7). A solution of 2 (0.16 g, 0.21 mmol)
in ca. 3 mL of benzene was treated with a solution of HOPh (0.020 g,
0.21 mmol) in ca. 1 mL of benzene at room temperature resulting in a
color change from red to pale yellow. The volatile components of the
reaction mixture were removed in vacuo, and the resulting residue was
washed with pentane (3 ꢁ 1 mL) to yield 7 (0.14 g, 84%) as a white
solid. 1H NMR (500 MHz, benzene-d6): δ 7.63 (br m, 2 H, Harom), 7.27
(br s, 2 H, Harom), 7.08 (br m, 2 H, Harom), 6.97 (br m, 2 H, Harom), 5.62
(br m, 2 H, Ru-η5-C6H5O), 5.14 (br d, 2 H, Ru-η5-C6H5O, J = 5 Hz),
3.98 (apparent t, 1 H, Ru-η5-C6H5O, J = 5 Hz), 2.46 (br m, 4 H, PCy),
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dx.doi.org/10.1021/ja204935x |J. Am. Chem. Soc. 2011, 133, 13622–13633