Organometallics
Article
2.20 (m, 23H, PMDETA), 2.36 (s, 3H, −C(Me)), 3.05 (d, 3JH−P
=
Synthesis of 10 [Ph2PCHCHCMe2Li(PMDETA)]. 3,3-Dimethy-
lallyldiphenylphosphine (P2) (0.2543 g, 1.00 mmol) was dissolved in
dry n-hexane (10 mL). n-Butyllithium (0.69 mL, 1.6 M in hexane, 1.1
mmol) was then added dropwise at −78 °C, forming yellow solution.
After warming to room temperature and stirring for a further 2 h,
PMDETA (0.23 mL, 1.1 mmol) was added dropwise with stirring,
turning the solution a dark orange and forming orange precipitate.
The precipitate was washed with hexane (3 × 10 mL) before the
remaining solvent was removed under reduced pressure with the solid
isolated in an argon box (0.322 g, 72%). No crystals suitable for X-ray
24.9 Hz, 1H, P−CH−), 3.96 (s, 1H, CHH), 4.05 (s, 1H, CHH),
7.13 (m, 2H, p-H), 7.25 (m, 4H, m-H), 8.32 (m, 4H, o-H). 7Li NMR
(C6D6, 155.53 MHz): δ −3.99. 13C NMR (C6D6, 100.6 MHz): δ
2
28.31 (d, JC−P = 17.6 Hz, −C(Me)), 44.15 (s, PMDETA), 45.58
1
(s, PMDETA), 48.52 (d, JC−P = 142.1 Hz, P−CH−), 53.47 (s,
3
PMDETA), 57.20 (s, PMDETA), 81.78 (d, JC−P = 6.6 Hz, CH2),
2
127.80 (m, m-C), 128.90 (s, p-C), 132.55 (d, JC−P = 8.7 Hz, o-C),
142.52 (d, 1JC−P = 105.0 Hz, −C(Me)), 149.23 (d, 2JC−P = 7.1 Hz,
i-C). 31P{H} NMR (C6D6, 162.0 MHz): δ 26.1. C25H39LiN3OP
(435.50): calcd C 68.95, H 9.03, N 9.65. Found C 68.23, H 9.00, N
9.46. Due to the highly sensitive nature of this compound, elemental
analysis within 0.4% was not attained. A difference within 0.72% in C
was the closest obtained.
1
diffraction were acquired. H NMR (C6D6, 400.20 MHz): δ 1.50−
1.85 (m, 23H, PMDETA) 2.07 (m, 6H, CMe2), 2.63 (dd, 3JH−H
=
2
3
13.0 Hz, JH−P = 7.5 Hz, 1H, P−CH−), 6.37 (t, JH−H = 13.0 Hz,
3JH−P = 12.5 Hz, 1H, −CH), 7.06 (m, 2H, p-H), 7.20 (m, 4H, m-
H), 7.87 (m, 4H, o-H). 7Li NMR (C6D6, 155.53 MHz): δ −4.50. 13
C
Synthesis of 8 [Ph2P(O)CHCHCMe2Li(PMDETA)]. 3,3-Dime-
thylallyldiphenylphosphine oxide (P2′) (0.2703 g, 1.00 mmol) was
loaded into a flask and suspended in dry Et2O (10 mL). n-
Butyllithium (0.69 mL, 1.6 M in hexane, 1.1 mmol) was then added
dropwise at −78 °C, forming a bright red solution. After warming to
room temperature and stirring for a further 2 h, PMDETA (0.23 mL,
1.1 mmol) was added dropwise with stirring, turning the solution dark
red. After 5 min, precipitate appeared in the mixture. The residue was
extracted with hexane (10 mL) before being filtered. The solvent was
removed under reduced pressure, and the dark red solid isolated in an
argon box (0.373 g, 83%). Crystals suitable for X-ray diffraction were
grown from a concentrated solution in Et2O layered with hexane at
4
NMR (C6D6, 100.6 MHz): δ 19.71 (d, JC−P = 3.1 Hz,
4
CMeMe(trans)), 27.39 (d, JC−P = 2.6 Hz, CMeMe(cis)), 37.24
(br m, P−CH−), 44.55 (s, PMDETA), 45.86 (s, PMDETA), 53.48
3
(s, PMDETA), 57.22 (s, PMDETA), 95.94 (d, JC−P = 23.3 Hz,
3
CMe2), 125.93 (s, p-C), 127.69 (d, JC−P = 5.3 Hz, m-C), 132.87 (d,
2
2JC−P = 16.9 Hz, o-C), 136.79 (d, JC−P = 28.1 Hz, −CH), 151.88
(d, 1JC−P = 19.7 Hz, i-C). 31P{H} NMR (C6D6, 162.00 MHz): δ −2.5.
C26H41LiN3P (433.55): calcd C 72.03, H 9.53, N 9.69. Found C
71.21, H 9.26, N 9.41. Due to the highly sensitive nature of this
compound, elemental analysis within 0.4% was not attained. A
difference within 0.82% in C was the closest obtained.
Synthesis of 11 [Ph2PCHC(Me)CH2Li(TMEDA)]. 2-Methylallyl-
diphenylphosphine (P3) (0.2403 g, 1.00 mmol) was dissolved in dry
n-hexane (10 mL). n-Butyllithium (0.69 mL, 1.6 M in hexane, 1.1
mmol) was then added dropwise at −78 °C, forming a slightly yellow
solution with a small amount of yellow precipitate. After warming to
room temperature and stirring for a further 2 h, TMEDA (0.17 mL,
1.1 mmol) was added dropwise with stirring, turning the solution
orange and forming yellow precipitate. The precipitate was washed
with hexane (3 × 10 mL) before the remaining solvent was removed
under reduced pressure with the solid isolated in an argon box (0.254
1
room temperature as red needles. H NMR (C6D6, 400.20 MHz): δ
1.61−2.17 (m, 23H, PMDETA), 2.17 (br-s, 6H, CMe2), 3.16 (dd,
3
3JH−P = 20.0 Hz, JH−H = 12.7 Hz, 1H, P−CH−), 6.24 (dd, JH−P
=
13.0 Hz, JH−H = 12.7 Hz, 1H, −CH), 7.11 (m, 2H, p-H), 7.23 (m,
7
4H, m-H), 8.41 (m, 4H, o-H). Li NMR (C6D6, 155.53 MHz): δ
−3.94. 13C NMR (C6D6, 100.6 MHz): δ 19.02 (s, CMe2), 27.05 (s,
1
CMe2), 44.20 (s, PMDETA), 44.21 (d, JC−P = 147.2 Hz, P−
CH−), 45.60 (s, PMDETA), 53.43 (s, PMDETA), 57.12 (s,
3
3
PMDETA), 96.61 (d, JC−P = 21.3 Hz, CMe2) 127.61 (d, JC−P
=
10.6 Hz, m-C), 128.90 (s, p-C), 129.49 (d, 2JC−P = 9.1 Hz, −CH),
1
g, 70%). No crystals suitable for X-ray diffraction were acquired. H
2
1
133.41 (d, JC−P = 8.2 Hz, o-C), 142.90 (d, JC−P = 106.8 Hz, i-C).
31P{H} NMR (C6D6, 162.0 MHz): δ 28.9. Due to the highly sensitive
nature of this compound, satisfactory elemental analysis was not
possible.
NMR (C6D6, 400.20 MHz): δ 1.56 (br-s, 4H, TMEDA−CH2), 1.73
(br-s, 12H, TMEDA−CH3), 2.34 (br-s, 3H, −C(Me)), 3.27 (br-s,
1H, −C(Me)CHH), 3.34 (br-s, 1H, −C(Me)CHH), 3.55 (br-s,
1H, P−CH−), 7.08 (m, 2H, p-H), 7.20 (m, 4H, m-H), 7.82 (m, 4H,
7
o-H). Li NMR (C6D6, 155.53 MHz): δ −4.47. 13C NMR (C6D6,
Synthesis of 9 [Ph2P(O)CHCHCH2Li(PMDETA)]. Allyldiphenyl-
phosphine oxide (P1′) (ADPPO) (0.2423 g, 1.00 mmol) was loaded
into a flask and suspended in dry Et2O (10 mL). n-Butyllithium (0.69
mL, 1.6 M in hexane, 1.1 mmol) was then added dropwise at −78 °C,
forming an orange solution. After warming to room temperature and
stirring for a further 2 h, PMDETA (0.23 mL, 1.1 mmol) was added
dropwise with stirring, turning the solution bright red. The majority of
the solvent was removed under reduced pressure, and the solution
was precipitated with hexane (10 mL) before being filtered.
Remaining solvent was removed under reduced pressure, and the
red solid isolated in an argon box (0.277 g, 66%). Crystals suitable for
X-ray diffraction were grown from a concentrated solution in Et2O
100.6 MHz): δ 23.06 (br-m, −C(Me)), 45.71 (s, TMEDA−CH3),
55.02 (br-m, CH2), 56.45 (s, TMEDA−CH2), 67.37 (br-m, P−
CH−), 126.52 (br-s, p-C), 128.00 (m, m-C), 132.66 (br-s, o-C),
150.01 (br-m, −C(Me)), 157.43 (br-m, i-C). 31P{H} NMR (C6D6,
1
162.00 MHz): δ −32.7, −27.6, −19.7. H NMR (THF-d8, 400.20
MHz): δ 1.93 (s, 3H, −C(Me)), 2.15 (s, 12H, TMEDA−CH3),
2.31 (s, 4H, TMEDA−CH2), 2.73 (br-s, 1H, CHH), 2.97 (br-s,
1H, P−CH−), 3.18 (br-s, 1HCHH), 7.00 (m, 2H, p-H), 7.09 (m,
7
4H, m-H), 7.36 (m, 4H, o-H). Li NMR (THF-d8, 155.53 MHz): δ
−6.82. 13C NMR (THF-d8, 100.6 MHz): δ 24.55 (br-m, −C(Me)),
46.31 (s, TMEDA−CH3), 56.53 (br-m, P−CH−), 58.91 (s,
TMEDA−CH2), 67.13 (br-m, CH2), 126.21 (s, p-C), 127.86 (d,
3JC−P = 5.6 Hz, m-C), 132.82 (d, 2JC−P = 18.0 Hz, o-C), 150.16 (br-m,
1
layered with hexane at room temperature as red needles. H NMR
(C6D6, 400.20 MHz): δ 1.74−2.37 (m, 23H, PMDETA), 3.70 (dd,
2JH−P = 21.6 Hz, 3JH−H(β) = 12.6 Hz, 1H, P−CH−) 4.21 (dt, 3JH−H(β)
= 9.85 Hz, 3JH−H(trans) = 3.7 Hz, 1H, −CHCHH), 4.63 (dd, 3JH−H(β)
2
i-C), 158.24 (d, JC−P = 29.1 Hz, −C(Me)). 31P{H} NMR (THF-
d8, 162.00 MHz): δ −17.4. Due to the highly sensitive nature of this
compound, satisfactory elemental analysis was not possible.
3
= 15.89 Hz, JH−H(cis) = 3.3 Hz, 1H, −CHCHH), 6.88 (tdd,
Synthesis of 12 [Ph2P(O)CHCHCH2Li·Et2O]. Allyldiphenylphos-
phine oxide (P1′) (0.2423 g, 1.00 mmol) was loaded into a flask and
suspended in dry Et2O (10 mL). n-Butyllithium (0.69 mL, 1.6 M in
hexane, 1.1 mmol) was then added dropwise at −78 °C, forming an
orange solution. After warming to room temperature, it was allowed
to stir for a further 2 h. The majority of the solvent was removed
under reduced pressure, and the solution was precipitated with hexane
(10 mL) before the supernatant was filtered off. Remaining solvent
was removed under reduced pressure, and the red solid was isolated in
an argon box (0.130 g, 42%). No crystals suitable for X-ray diffraction
were acquired. 1H NMR (C6D6, 400.20 MHz): δ 1.06 (br-t, 6H,
Et2O−CH3), 3.22 (br-q, 4H, Et2O−CH2), 3.37 (dd, 2JH−P = 21.0 Hz,
3
3
3JH−H(trans) = 15.89 Hz, JH−H(α) = 12.63 Hz, JH−H(cis) = 9.85 Hz, 1H,
−CHCH2), 7.11 (m, 2H, p-H), 7.23 (m, 4H, m-H), 8.36 (m, 4H,
7
o-H). Li NMR (C6D6, 155.53 MHz): δ −3.94. 13C NMR (C6D6,
100.6 MHz): δ 44.05 (br s, PMDETA), 45.77 (s, PMDETA), 51.22
1
(d, JC−P = 146.5 Hz, P−CH−), 53.56 (s, PMDETA), 57.38 (s,
3
3
PMDETA), 81.58 (d, JC−P = 21.8 Hz, CH2), 127.71 (d, JC−P
=
10.9 Hz, m-C), 129.13 (d, 4JC−P = 2.6 Hz, p-C), 133.30 (d, 2JC−P = 8.4
1
2
Hz, o-C), 141.82 (d, JC−P = 8.1 Hz, i-C), 142.06 (d, JC−P = 106.8
Hz, −CH). 31P{H} NMR (C6D6, 162.0 MHz): δ 29.2. Due to the
highly sensitive nature of this compound, satisfactory elemental
analysis was not possible.
I
Organometallics XXXX, XXX, XXX−XXX