6544 Organometallics, Vol. 27, No. 24, 2008
Field et al.
solid was dried in Vacuo. The product was recrystallized from
acetone/pentane to give cis-[Ru(η3-PhCt CCdC(H)Ph)(PMe3)4]BF4
(6) as a yellow solid. Yield: 0.094 g (0.134 mmol, 60%). 1H NMR
(200 MHz, acetone-d6): δ 7.77 (m, 4H, ArH), 7.58-7.37 (m, 5H,
ArH), 7.27 (m, 1H, ArH), 7.17 (d, 4JPH ) 4.6 Hz, 1H, CdC(Ph)H),
1.86 (d, 2JPH ) 8.6 Hz, 9H, Peq(CH3)3), 1.81 (d, 2JPH ) 7.9 Hz, 9H,
1171, 1055, 1033, 971, 944, 860 cm-1. The product was recrystal-
lized from acetone/pentane to yield crystals suitable for microanaly-
sis. Anal. Calcd for C30H51BF4O2P4Ru · (CH3)2CO: C, 48.72; H,
7.06. Found: C, 48.85; H, 7.02.
cis-[Ru(η3-tBuCt CCdC(H)tBu)(PMe3)4]BF4 (10). Prepared as
described for 7, from Ru(Ct CtBu)2(PMe3)4 (4) (0.239 g, 0.549
mmol) and 2,6-lutidinium tetrafluoroborate (0.1058 g, 0.543 mmol).
Peq(CH3)3), 1.20 (apparent t, splitting ) 3.5 Hz, 18H, Pax(CH3)3)
2
ppm. 31P{1H} NMR (121 MHz, acetone-d6): δ -2.72 (dt, JPP
)
1
Yield: 0.286 g (0.430 mmol, 79%). H NMR (300 MHz, acetone-
2
2
2
d6): δ 5.87 (m, 1H, dC(H)tBu), 1.82 (d, JPH ) 8.7 Hz, 9H,
20.7 Hz, JPP ) 34.6 Hz, 1P, Peq), -12.43 (dd, JPP ) 30.6 Hz,
2
2
2JPP ) 34.6 Hz, 2P, 2 × Pax), -19.87 (dt, JPP ) 20.7 Hz, JPP
)
2
P(CH3)3), 1.72 (d, JPH ) 8.7 Hz, 9H, P(CH3)3), 1.50 (s, 9H,
30.6 Hz, 1P, Peq) ppm. 13C{1H} NMR (75 MHz, acetone-d6): δ
148.4 (d, 2JPC ) 42.9 Hz, Ru-CdC), 138.9 (ArCipso), 132.6 (ArCpara),
130.7 (CdC(H)Ph), 130.1, 129.8, 129.43, 129.39 (ArCipso), 127.7,
126.9 (ArCpara), 115.4 (d, 2JPC ) 28.3 Hz, PhCt C), 59.7 (PhCt C),
C(CH3)3), 1.26 (m, 27H, P(CH3)3 and C(CH3)3) ppm. 31P{1H} NMR
2
2
(121 MHz, acetone-d6): δ 5.52 (dt, JPP ) 15.7 Hz, JPP ) 36.8
Hz, 1P, Peq), -14.26 (dd, 2JPP ) 30.3 Hz, 2JPP ) 36.8 Hz, 2P, 2 ×
2
2
Pax), -18.01 (dt, JPP ) 15.7 Hz, JPP ) 30.3 Hz, 1P, Peq) ppm.
13C{1H} NMR (151 MHz, acetone-d6): δ 141.5 (CdC(H)tBu), 139.5
(d, 2JPC ) 51.4 Hz, Ru-CdC), 118.7 (d, 2JPC ) 23.7 Hz, (Ct CtBu),
55.3 (Ct CtBu), 33.6 (C(CH3)3), 33.3 (C(CH3)3), 30.7 (C(CH3)3),
1
1
24.9 (d, JPC ) 26.5 Hz, Peq(CH3)3), 23.8 (d, JCP ) 30.3 Hz,
Peq(CH3)3), 18.3 (apparent t, splitting ) 13.3 Hz, Pax(CH3)3) ppm.
MS(ESI) m/z: 533 (25%) [M - P(CH3)3]+, 457 (100) [M -
2P(CH3)3]+, 381 (27) [M - 3P(CH3)3]+. νmax (KBr disk): 2975,
2912, 2051, 1591, 1482, 1423, 1307, 1285, 1084, 1055, 1037, 945,
860, 763, 720, 697, 669 cm-1. Anal. Calcd for C28H47BF4P4Ru: C,
48.36; H, 6.81. Found: C, 48.62; H, 6.93.
1
1
30.4 (C(CH3)3), 26.8 (d, JPC ) 24.0 Hz, Peq(CH3)3), 23.7 (d, JPC
) 30.7 Hz, Peq(CH3)3), 18.9 (apparent t, splitting ) 13.7 Hz,
Pax(CH3)3) ppm. MS(ESI) m/z (abundance): 493 (100) [M -
PMe3]+. νmax (KBr disk): 2963, 2909, 1427, 1305, 1286, 1232, 1084,
1055, 1036, 953, 864, 716, 667 cm-1
. Anal. Calcd for
cis-[Ru(η3-(p-C6H4 -Me)Ct CCdC(H)(p-C6H4-Me))(PMe3)4]-
BF4 (8). Prepared as described for 7 from Ru(Ct C(p-C6H4-
Me))2(PMe3)4 (2) (0.171 g, 0.393 mmol). Yield: 0.134 g (0.188
C24H55BF4P4Ru: C, 43.98; H, 8.46. Found: C, 43.91; H, 8.71.
Crystals suitable for X-ray diffraction were grown by layering an
acetone solution of the complex with heptane.
1
mmol, 48%). H NMR (300 MHz, acetone-d6): δ 7.70 (m, 4H,
cis-[Ru(η3-Me3SiCt CCdC(H)SiMe3)(PMe3)4]BF4 (11). Tri-
methylsilylacetylene (0.54 mL, 3.82 mmol) was added to a solution
of RuMe2(PMe3)4 (0.1645 g, 0.377 mmol) in THF (10 mL). The
mixture was stirred at 50 °C for 2 h, after which time the volatiles
were removed under reduced pressure. The pale brown residue was
dissolved in THF (10 mL), and 2,6-lutidinium tetrafluoroborate
(0.0716 g, 0.361 mmol) was added as a single solid portion. A
suspension was quickly formed. The mixture was stirred overnight
at room temperature before the dark green mother liquor was
decanted from the precipitate. The residue was dried in Vacuo to
yield cis-[Ru(η3-Me3SiCt CCdC(H)SiMe3)(PMe3)4]BF4 (11) as a
ArH), 7.35 (m, AA′ of AA′XX′, 2H, ArH), 7.25 (m, XX′ of
AA′XX′, 2H, ArH), 7.09 (d, 4JPH ) 4.3 Hz, 1H, CdC(H)Ar), 2.40
(s, 3H, Ar-CH3), 2.33 (s, 3H, Ar-CH3), 1.84 (m, 18H, Peq(CH3)3),
1.21 (m, 18H, Pax(CH3)3) ppm. 31P{1H} NMR (121 MHz, acetone-
2
2
d6): δ 1.25 (dt, JPP ) 20 Hz, JPP ) 34 Hz, 1P, Peq), -8.40 (dd,
2JPP ) 29 Hz, 2JPP ) 34 Hz, 2P, 2 × Pax), -15.9 (dt, 2JPP ) 20 Hz,
2JPP ) 29 Hz, 1P, Peq) ppm. 13C{1H} NMR (75 MHz, acetone-d6):
δ 147.0 (Ru-C), 139.6 (ArC-CH3), 137.5 (ArC-CH3), 136.6 (Ar-
Cipso), 132.7 (ArCortho), 130.9 (ArCmeta), 130.5 (ArCmeta), 130.4
(CdC(H)Ar), 126.9 (ArCortho), 126.3 (ArCipso), 114.6 (Ct CAr), 58.9
(Ct CAr), 25.1 (d, 1JPC ) 25.7 Hz, Peq(CH3)3), 24.0 (d, 1JPC ) 30.0
Hz, Peq(CH3)3), 21.4 (C-CH3), 21.2 (C-CH3), 18.4 (apparent t,
splitting ) 13.8 Hz, Pax(CH3)3) ppm. MS(ESI) m/z (abundance):
561 (100) [M - PMe3]+. νmax (KBr disk): 2976, 2913, 1506, 1423,
1
pale yellow solid. Yield: 0.165 g (0.259 mmol, 69%). H NMR
(300 MHz, acetone-d6): δ 6.82 (m, 1H, CdC(H)SiMe3), 1.82 (d,
2
2JPH ) 6.9 Hz, 9H, Peq(CH3)3), 1.74 (d, JPH ) 8.7 Hz, 9H,
1308, 1287, 1083, 1051, 1037, 944, 860, 815, 718, 669, 522 cm-1
.
Peq(CH3)3), 1.21 (apparent t, splitting ) 3.06 Hz, 18H, Pax(CH3)3),
0.43 (s, 9H, Si(CH3)3), 0.23 (s, 9H, Si(CH3)3) ppm. 31P{1H} NMR
Anal. Calc for C30H51BF4P4Ru: C, 49.80; H, 7.11. Found: C, 49.98;
H, 7.03.
2
2
(121 MHz, acetone-d6): δ 8.29 (dt, JPP ) 15.6 Hz, JPP ) 35.2
Hz, 1P, Peq), -10.35 (m, 2P, 2 × Pax), -13.26 (m, 2P, Peq) ppm.
13C{1H,31P} NMR (75 MHz, acetone-d6): δ 170.7 (Ru-CdC), 137.2
(CdC(H)SiMe3), 110.9 (Ct CSiMe3), 81.5 (Ct CSiMe3), 26.7
(Peq(CH3)3), 23.5 (Peq(CH3)3), 18.5 (Pax(CH3)3), 2.2 (Si(CH3)3), -0.6
(Si(CH3)3) ppm. MS(ESI) m/z (abundance): 525.1 (100) [M -
P(CH3)3]+. HRMS (LSIMS): 598.18351. Required for
C22H55P4Si299Ru: 598.19351. νmax (KBr disk): 3642, 2953, 2910,
cis-[Ru(η3-(p-C6H4-OMe)Ct CCdC(H)(p-C6H4OMe)(PMe3)4]-
BF4 (9). Prepared as described for 7, from Ru(Ct C(p-C6H4-
OMe))2(PMe3)4 (3) (0.226 g, 0.338 mmol) and 2,6-lutidinium
tetrafluoroborate (0.066 g, 0.336 mmol). Concentration of the THF
solution under reduced pressure and cooling to -20 °C gave a bright
yellow microcrystalline solid. Yield: 0.189 g (0.251 mmol, 74%).
1H NMR (600 MHz, acetone-d6): δ 7.77 (m, AA′ of AA′XX′, 2H,
ArHortho), 7.72 (m, AA′ of AA′XX′, 2H, ArHortho), 7.10 (m, XX′ of
1636, 1588, 1428, 1307, 1289, 1242, 1063, 949, 836, 717, 668 cm-1
.
cis-[Ru(η3-MeCt CCdC(H)Me)(PMe3)4]BF4 (12a and 12b).
A mixture of Ru(Ct CMe)2(PMe3)4 (6) (0.0252 g, 0.0521 mmol)
and 2,6-lutidinium tetrafluoroborate (0.0070 g, 0.0506 mmol) was
dissolved in CD2Cl2. The color of the solution immediately turned
4
AA′XX′, 2H, ArHmeta), 7.03 (d, JPH ) 4.6 Hz, 1H, CdC(H)Ar),
7.01 (m, XX′ of AA′XX′, 2H, ArHmeta), 3.88 (s, 3H, OCH3), 3.83
2
(s, 3H, OCH3), 1.85 (d, JPH ) 8.5 Hz, 9H, Peq(CH3)3), 1.81 (d,
2JPH ) 7.2 Hz, 9H, Peq(CH3)3), 1.19 (apparent t, splitting ) 3.0
Hz, 18H, Peq(CH3)3) ppm. 31P{1H} NMR (121 MHz, acetone-d6):
1
yellow. 12a (E-stereochemistry): Selected H NMR (300 MHz,
2
2
CD2Cl2): δ 5.63 (apparent br pentet, splitting ) 4.9 Hz, 1H,
δ 1.75 (dt, JPP ) 19.3 Hz, JPP ) 33.7 Hz, 1P, Peq), -7.79 (dd,
3
2JPP ) 30.2 Hz, JPP ) 33.7 Hz, 2P, 2 × Pax), -15.1 (dt, JPP
)
2
2
dC(H)CH3), 2.39 (s, 3H, t CCH3), 2.05 (d, JHH ) 6.4 Hz, 3H,
dC(H)CH3), 1.62 (d, 2JPH ) 5.7 Hz, 9H, Peq(CH3)3), 1.55 (d, 2JPH
) 7.7 Hz, 9H, Peq(CH3)3), 1.06 (apparent t, splitting ) 3.0 Hz,
19.3 Hz, 2JPP ) 30.2 Hz, 1P, Peq) ppm. 13C{1H} NMR (151 MHz,
2
acetone-d6): δ 160.9 (C-OCH3), 159.9 (C-OCH3), 144.9 (dq, JPC
) 42.6, 2JPC ) 7.8 Hz, Ru-C ) C), 134.3 (ArCortho), 132.4 (d, 3JPC
) 4.8 Hz, CdC(H)Ar, 129.5 (ArCipso), 128.1 (ArCortho), 121.0
18H, 2 × Pax(CH3)3) ppm, phosphine proton resonances coincident
2
with 12b. 31P{1H} NMR (121 MHz, CD2Cl2): δ 5.03 (dt, JPP
)
15.5 Hz, 2JPP ) 33.1 Hz, 1P, Peq), -5.91 (apparent t, 2P, 2 × Pax),
-14.66 (dt, 2JPP ) 15.5 Hz, 2JPP ) 31.8 Hz, 1P, Peq) ppm. 13C{1H}
NMR (125 MHz, CD2Cl2): δ 149.6 (Ru-CdC), 124.9 (Ru-CdC),
102.1 (Ct CCH3), 44.8 (Ct CCH3), 25.7 (CdC(H)CH3), 24.6
(Peq(CH3)3), 24.3 (Peq(CH3)3), 18.1 (Pax(CH3)3), 11.5 (Ct CCH3)
ppm. 12b (Z-stereochemistry): Selected 1H NMR (300 MHz,
2
(ArCipso), 115.7 (ArCmeta), 115.3 (ArCmeta), 113.8 (d, JPC ) 24.8
Hz, Ct CAr), 57.5 (Ct CAr), 55.9 (O-CH3), 55.7 (O-CH3), 25.1
(d, JPC ) 25.1 Hz, Peq(CH3)3), 24.0 (dd, JPC ) 29.5 Hz, JPC
1
1
3
)
1.7 Hz, Peq(CH3)3), 18.4 (apparent t, splitting ) 14.0 Hz, Pax(CH3)3)
ppm. MS(ESI) m/z (abundance): 593.15 (100) [M -P(CH3)3]+. νmax
(KBr disk): 2974, 2912, 2837, 1598, 1506, 1438, 1306, 1284, 1248,