8626 Inorganic Chemistry, Vol. 48, No. 17, 2009
Greenberg and Stephan
3JP-C=4 Hz). 31P{1H} NMR (C6D6): δ 165.2. 13C{1H} NMR
(C6D6, partial): δ 143.7 (d, ipso-C, 1JP-C=26 Hz), 132.8 (s, Ar),
132.1 (s, Ar), 129.0 (s, Ar), 128.8 (s, Ar), 123.3 (s, Ar), 92.7
HRMS: C20H23P mass 294.1542; calcd mass 294.1537 (fit
1.74 ppm). FT-IR (25 °C, Nujol mull): ν(CtC) 2209 cm-1
(weak), ν(P-H) 2315 cm-1 (br). Anal. Calcd for C20H23P: C,
81.60; H, 7.88. Found: C, 81.10; H, 8.12. Crystals suitable for
X-ray diffraction could be obtained from the oil upon standing.
3
(s, CtC), 89.1 (s, CtC), 21.3 (d, Me, JP-C=26 Hz). FT-IR
(evaporation of a CH2Cl2 solution): ν(CtC) 2212 cm-1 (sharp).
Anal. Calcd for C16H13Cl2P: C, 62.57; H, 4.27. Found: C, 63.23;
H, 4.79. Crystals suitable for X-ray diffraction were obtained
from the oil upon standing.
12. Yield: 55%. 1H NMR (C6D6): δ 7.50 (d, 2H, C6H2, 4JP-H
=
2 Hz), 3.72 (d, 2H, PH2, 1JP-H=207 Hz), 3.23 (d of septets, 2H,
i-Pr, 3JH-H=7 Hz, 4JP-H=3 Hz), 1.01 (d, 12H, i-Pr, 3JH-H
7Hz), 0.28(s, 9H, Si(Me)3). 31PNMR(C6D6):δ-156.2 (t, 1JP-H
207 Hz). 13C{1H} NMR (C6D6, partial): δ152.1 (d, ipso-C, 1JP-C
=
=
=
1
8. Yield: 89%. H NMR (C6D6): δ 7.56-7.52 (m, 4H, o-Ph
and C6H2), 6.99-6.97 (m, 3H, m- and p-Ph), 4.12-4.06 (m, 2H,
i-Pr), 1.12 (d, 12H, i-Pr, 3JH-H=7 Hz). 31P{1H} NMR (C6D6): δ
=
9 Hz), 128.3 (s, Ar), 126.7 (s, Ar), 123.7 (s, quat-Ar), 106.7 (s,
CtCSiMe3), 94.5 (s, CtCSiMe3), 33.1 (d, i-Pr, 3JP-C=11 Hz),
23.3 (s, i-Pr), 0.127 (s, Si(Me)3). 29Si{1H} NMR (C6D6): δ -18.2
(s). EI-MS (70 eV; m/z): 290 (100%) [M]þ, 275 (72%) [M-Me]þ.
HRMS (70 eV, EI): calcd for C17H27P 290.1620; found 290.1606
(fit -4.8 ppm). FT-IR (evaporation of a CH2Cl2 solution):
ν(CtC) 2158 cm-1 (sharp), ν(P-H) 2320 cm-1 (br). Anal. Calcd
for C17H27PSi: C, 70.30; H, 9.37. Found: C, 70.58; H, 8.73.
Generation of Compound Li(THF)xHPC6H2-i-Pr2CtCPh
(13). Compound 11 (200 mg, 0.680 mmol) was placed in a 20 mL
scintillation vial inside a brass plate designed to surround the
bottom and walls of the vial. A total of 10 mL of THF was added,
and the entire assembly was cooled to -35 °C. n-BuLi in pentane
(0.44 mL of 1.7 mol/L, 0.75 mmol, 1.1 equiv) was added with
stirring, generating a red solution. The entire assembly was warmed
to room temperature over 4 h, and then all volatiles were removed in
vacuo, giving a red residue. Yield: 350 mg (95%). 1H NMR (C6D6):
δ 7.58-7.54 (m, 4H, o-Ph and C6H2), 7.03-6.94 (m, 3H, m- and
p-Ph), 3.90 (m, 2H, i-Pr), 3.52 (m, ca. 7.6H, THF), 2.92 (d, 2H, PH2,
1JP-H=182 Hz), 1.41 (d, 12H, i-Pr, 3JH-H=7 Hz), 1.37 (m, ca.
162.7. 13C{1H} NMR (C6D6, partial): δ 155.1 (d, ipso-C, 1JP-C
23 Hz), 135.6 (s, Ar), 134.6 (s, Ar), 132.1 (s, Ar), 129.1 (s, Ar),
128.8 (s, Ar), 123.2 (s, Ar), 92.6 (s, CtC), 89.6 (s, CtC), 30.9 (d,
3
i-Pr, JP-C =27 Hz), 24.4 (s, i-Pr). EI-MS (m/z): 362.1 (27%)
[M]þ; 327.1 (100%) [M]þ - Cl. HRMS: C20H21Cl2P mass
362.0753; calcd mass 362.0758 (fit -1.4 ppm). FT-IR (Nujol
mull): ν(CtC) 2209 cm-1 (sharp). Anal. Calcd for C20H21Cl2P:
C, 66.13; H, 5.83. Found: C, 66.32; H, 5.90. Crystals suitable for
X-ray diffraction were obtained from the oil upon standing.
9. Yield: 91.3%. 1H NMR (C6D6, 25 °C, 300 MHz): δ 7.48 (d,
2H, C6H2, 4JP-H=3 Hz), 4.03 (m, 2H, i-Pr), 1.02 (d, 12H, i-Pr,
3JH-H=7 Hz), 0.26 (s, 9H, Si(Me)3). 31P{1H} NMR (C6D6): δ
162.5. 13C{1H} NMR (C6D6, partial): δ 155.2 (d, ipso-C, 1JP-C
=
22 Hz), 129.3 (s, Ar), 125.7 (s, Ar), 105.3 (s, CtC), 97.4 (s,
3
CtC), 30.9 (d, i-Pr, JP-C = 27 Hz), 24.3 (s, i-Pr), -0.09 (s,
Si(Me)3. 29Si{1H} NMR (C6D6): δ -17.4 (s). EIMS (70 eV; m/z):
358 (48%) [M]þ, 343 (79%) [M-Me]þ, 323 (100%) [M-Cl]þ,
307 (35%) [M-Me-Cl-H]þ. HRMS (70 eV, EI): calcd for
C17H25Cl2PSi 358.0840; found 358.0823 (fit -4.7 ppm). FT-IR
(evaporation of a CH2Cl2 solution): ν(CtC) 2160 cm-1 (sharp).
Anal. Calcd for C17H25Cl2PSi: C, 56.82; H, 7.01. Found: C,
56.85; H, 6.93.
1
7.6H, THF). 31P NMR (C6D6): δ -162.5 (d, JP-H = 182 Hz).
13C{1H} NMR (C6D6): δ 147.8 (d, ipso-C, 1JP-C=6 Hz), 132.0 (s,
Ar), 131.7 (s, Ar), 127.3 (s, Ar), 125.5 (s, Ar), 124.9 (s, Ar), 114.4 (s,
Ar), 93.8 (s, CtC), 88.2 (s, CtC), 68.1 (THF), 33.0 (d, i-Pr, 3JP-C
=
Synthesis of H2PC6H2R2CtCR0 (10, R=Me, R0=Ph; 11, R=
i-Pr, R0 =Ph; 12, R=i-Pr, R0 =SiMe3). All compounds were
prepared in a similar manner; thus, only the synthesis of 11 is
reported. An orange solution of 8 (1.760 g, 4.845 mmol) in 20 mL
of Et2O and 20 mL of toluene was added dropwise via cannula
over 30 min to a -78 °C slurry of LiAlH4 (1.014 g, 26.72 mmol,
5.5 equiv) in 70 mL of Et2O. The mixture was stirred overnight
while warming to 25 °C. The brown mixture was cooled again in an
ice-water bath, and 10 mL of degassed water was added dropwise,
resulting in gas formation. The organic layer was transferred by
cannula to a flask containing MgSO4. The aqueous layer was
extracted with two portions of 20 mL of Et2O, and all organic
portions were combined in the flask containing MgSO4. The yellow
solution was then transferred via cannula to a Schlenk frit and
filtered. Upon removal of all volatiles in vacuo, a yellow residue was
obtained.
14 Hz), 25.7 (THF), 23.9 (s, i-Pr). 7Li{1H} NMR (C6D6): δ -0.7.
Synthesis of R(H)PC6H2(i-Pr)2CtCPh [R = CH2i-Pr (14),
CH2Ph (15)]. These compounds were prepared in a similar
manner; thus, only the synthesis of 14 is reported. Compound
13 was generated as above. The entire assembly was warmed to
25 °C over 4 h, then BrCH2i-Pr (88 mg, 0.64 mmol, 1.0 equiv), as
well as 4 mL of toluene, was added dropwise, and the reaction
mixture was stirred overnight. The orange-brown mixture was
filtered through Celite, and all volatiles were removed in vacuo,
yielding a brown oil.
1
14. Yield: 179 mg. H NMR (C6D6): δ 7.62-7.57 (m, 4H,
o-Ph and C6H2), 7.03-6.97 (m, 3H, m- and p-Ph), 4.36 (ddd,
1H, PH, 1JP-H=212 Hz, 3JH-H=9 Hz, 3JH-H=6 Hz), 3.78-
3.67 (m, 2H, Ar-i-Pr), 1.86-1.76 (m, 1H, PCHaHb), 1.74-1.64
(m, 1H, PCH2-i-Pr), 1.49-1.37 (m, 1H, PCHaHb), 1.20 (d, 6H,
10. Yield: 44%. 1H NMR (C6D6): δ 7.58-7.56 (m, 2H, o-Ph),
7.21 (s, 2H, C6H2), 7.04-6.98 (m, 3H, m- and p-Ph), 3.50 (d, 2H,
PH2, 1JP-H=207 Hz), 2.03 (d, 6H, Me, 4JP-H=9 Hz). 31P NMR
ArCH(Me)a(Me)b, JH-H = 7 Hz), 1.13 (d, 6H, ArCH(Me)a-
3
(Me)b, 3JH-H=7 Hz), 0.97 (d, 3H, PCH2CH(Me)a(Me)b, 3JH-H
=
3
4 Hz), 0.94 (d, 3H, PCH2CH(Me)a(Me)b, JH-H =4 Hz). 31P
1
1
(C6D6): δ -153.8 (t, JP-H =207 Hz). 13C{1H} NMR (C6D6,
NMR (C6D6): δ -99.0 (d, JP-H = 212 Hz). 13C{1H} NMR
partial): δ 141.0 (d, ipso-C, 1JP-C=11 Hz), 131.9 (s, Ar), 130.9
(s, Ar), 124.1 (s, Ar), 122.7 (s, Ar), 90.2 (s, CtC), 22.9 (d, Me,
3JP-C=10 Hz). EI-MS (m/z): 238.1 (100%) [M]þ; 223.1 (60%)
[M]þ-Me. HRMS: C16H15P mass 238.0911; calcd mass 238.0902
(fit -3.8 ppm). FT-IR (Nujol mull): ν(CtC) 2211 cm-1 (weak),
ν(P-H) 2306 cm-1 (sharp). Despite repeated attempts, suitable
elemental analysis could not be obtained.
(C6D6): δ 153.5 (d, ipso-C, 1JP-C=11 Hz), 133.9 (s, Ar), 133.6 (s,
Ar), 132.0 (s, Ar), 128.7 (s, Ar), 126.9 (s, Ar), 124.6 (s, Ar), 124.1
(s, Ar), 90.9 (s, CtC), 90.4 (s, CtC), 34.2 (d, PCH2-i-Pr, 1JP-C
=
3
13 Hz), 33.0 (d, Ar-i-Pr, JP-C =13 Hz), 28.4 (d, PCH2-i-Pr,
2JP-C = 12 Hz), 24.7 (s, ArCH(Me)a(Me)b), 24.3 (s, ArCH-
(Me)a(Me)b), 23.94 (s, PCH2-i-Pr), 23.86 (s, PCH2-i-Pr). EI-MS
(m/z): 350.2 (37%) [M]þ; 293.1 (100%) [M]þ-CH2-i-Pr. HRMS:
C24H31P mass 350.2164; calcd mass 350.2163 (fit 0.3 ppm). FT-
IR (Nujol mull): ν(CtC) 2209 cm-1 (sharp), ν(P-H) 2320 cm-1
(br). Despite repeated attempts, suitable elemental analysis
could not be obtained.
11. Yield: 70% 1H NMR (C6D6): δ 7.60-7.57 (m, 2H, o-Ph),
4
7.54 (d, 2H, C6H2, JP-H =2 Hz), 7.00-6.89 (m, 3H, m- and
p-Ph), 3.77 (d, 2H, PH2, 1JP-H=206 Hz), 3.23 (d of septets, 2H,
i-Pr, 3JH-H=7 Hz, 4JP-H=3 Hz), 1.08 (d, 12H, i-Pr, 3JH-H
=
7 Hz). 31P NMR (C6D6): δ -156.3 (t, 1JP-H=207 Hz). 13C{1H}
NMR (C6D6, partial): δ 152.2 (d, ipso-C, 1JP-C=9 Hz), 132.0 (s,
Ar), 128.7 (s, Ar), 126.5 (s, Ar), 124.1 (s, Ar), 123.9 (s, Ar) 90.9 (s,
CtC), 90.3 (s, CtC), 33.1 (d, i-Pr, 3JP-C=11 Hz), 23.4 (s, i-Pr).
EI-MS (m/z): 294.2 (100%) [M]þ; 251.1 (83%) [M]þ - i-Pr.
15. Yield: 50%. 1H NMR (C6D6): δ 7.58-7.56 (m, 4H, ArH),
7.03-6.91 (m, 8H, ArH), 4.54 (dt, 1H, PH, 1JP-H=214 Hz, 3JH-
H=7 Hz), 3.50-3.44 (m, 2H, i-Pr), 2.89 (m, 2H, PCH2Ph), 1.09
(d, 12H, i-Pr, 3JH-H=6 Hz). 31PNMR(C6D6):δ-80.9(d, 1JP-H
=
214 Hz). 13C{1H} NMR (C6D6, partial): δ 153.6 (d, ipso-C,