Organometallics
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removed under vacuum, and the resulting crude product was triturated
with anhydrous Et2O (3×) to give the desired product as an off-white
solid (84 mg, 95% yield). The product was recrystallized using
CH2Cl2/Et2O at −20 °C.
(d, J = 6.1 Hz), 135.0 (d, J = 1 Hz), 133.8 (d, J = 7.3 Hz), 133.7, 131.7
(d, J = 1.9 Hz), 130.33, 130.3, 130.2, 129.7, 129.4, 129.0, 128.6, 128.1,
127.9 (d, J = 6.5 Hz), 127.6, 126.5 (d, J = 41.6 Hz), 126.1, 55.9 (d, J =
46.2 Hz), 48.9, 44.8, 38.33 (d, J = 22.2 Hz), 38.2 (d, J = 21.7 Hz), 31.3
(d, J = 6.6 Hz), 31.0 (d, J = 6.6 Hz), 16.0 (d, J = 4.3 Hz), 13.9, 12.7.
31P NMR (120 MHz, CD2Cl2): δ 64.6. Anal. Calcd (found) for
C33H46AuF6NPSb: C, 43.06 (43.20); H, 5.04 (5.08); N, 1.52 (1.50).
1H NMR (300 MHz, CD2Cl2): δ 7.90−7.79 (m, 1H), 7.58−7.18
(m, 8H), 5.82 (br s, 1H), 3.46−3.41 (m, 4H), 1.89 (d, J = 1 Hz, 3H),
1.83 (d, JHP = 9 Hz, 2H), 1.71 (d, J = 0.5 Hz, 3H), 1.37 (d, JHP = 15.4
Hz, 18H), 1.30 (t, 3H, J = 7.2 Hz), 1.11 (t, J = 7.2 Hz, 3H). 13C NMR
(125 MHz, CD2Cl2): δ 183.5 (d, J = 3.7 Hz), 149.7 (d, JCP = 14.8 Hz),
144.3 (d, JCP = 6.4 Hz), 143.9 (CCMe2), 134.9 (d, JCP = 1.8 Hz),
133.7 (d, JCP = 7.6 Hz), 131.5 (d, JCP = 2.3 Hz), 130.4, 129.0, 128.0 (d,
JCP = 6.2 Hz), 127.5, 126.8 (d, JCP = 40.8 Hz), 119.7 (CCMe2), 47.6,
45.6, 45.2 (d, JCP = 48.5 Hz), 38.0 (d, JCP = 22.1 Hz), 31.2 (d, JCP = 6.6
Hz), 25.8, 20.7, 13.3 (d, J = 1.25 Hz), 12.5. 31P NMR (120 MHz,
CD2Cl2): δ 65.5 ppm. Anal. Calcd (found) for C30H46AuF6NPSb: C,
40.74 (40.86); H, 5.24 (5.18); N, 1.58 (1.59).
−
[(t-Bu)2(o-biphenyl)PAu][1-(cyclohex-1-en-1-yl)pyrrolidine]+SbF6
(5). Complex 5 was prepared according to the procedure to prepare 1.
The product was obtained as an off-white solid (70% yield). The
product was recrystallized with CH2Cl2/Et2O at −20 °C.
1H NMR (500 MHz, CD2Cl2): δ 7.89−7.86 (m, 1H), 7.61−7.48
(m, 5H), 7.29−7.14 (m, 3H), 3.37−3.70 (m, 1H), 3.44−3.36 (m, 2H),
3.17−3.09 (m, 1H), 2.80−2.27 (m, 2H), 2.06−1.60 (m, 11H), 1.42 (d,
9H, JHP = 15.5 Hz), 1.25 (d, 9H, JHP = 15.3 Hz). 13C NMR (125 MHz,
CD2Cl2): δ 179.4 (d, JCP = 3.6 Hz), 149.5 (d, JCP = 14.8 Hz), 144.0 (d,
JCP = 6.2 Hz), 134.7, 133.5 (d, JCP = 7.6 Hz), 131.5 (d, JCP = 1.9 Hz),
130.2, 130.1, 129.0, 128.9, 127.9 (d, JCP = 6.5 Hz), 127.8, 126.4 (d, JCP
= 40.1 Hz), 59.6 (d, JCP = 45.5 Hz), 50.8, 50.1, 38.2 (d, JCP = 21.3 Hz),
37.9 (d, JCP = 21.6 Hz), 31.1 (d, JCP = 6.4 Hz), 30.8 (d, JCP = 6.5 Hz),
27.6, 27.5, 25.4, 24.9, 23.6, 23.5. 31P NMR (120 MHz, CD2Cl2): δ
66.1. Anal. Calcd (found) for C30H44AuF6NPSb: C, 40.84 (40.93); H,
5.03 (4.99); N, 1.59 (1.54).
[(t-Bu)2(o-biphenyl)PAu][N,N-diethyl-1-phenylethene-1-ami-
−
ne]+SbF6 (2). Complex 2 was prepared according to the procedure to
prepare 1. The product was obtained as an off-white solid (≥99%).
The product was recrystallized with CH2Cl2/Et2O at −20 °C.
1H NMR (500 MHz, CD2Cl2): δ 7.94−7.88 (m, 1H), 7.57−7.46
(m, 5H), 7.36−7.09 (m, 8H), 3.60 (q, J = 6.9 Hz, 2H), 3.33 (q, 2H, J =
7.3 Hz), 1.90 (d, JHP = 8.8 Hz, 2H), 1.42 (t, J = 7.3 Hz, 3H), 1.41 (d,
JHP = 15.4 Hz, 18H), 1.08 (t, J = 7.1 Hz, 3H). 13C NMR (125 MHz,
CD2Cl2): δ 187.7 (d, J = 3.3 Hz), 149.5 (d, JCP = 14.7 Hz), 144.1 (d,
JCP = 6.2 Hz), 136.1, 134.7, 133.5 (d, JCP = 7.7 Hz), 131.3 (d, JCP = 2.3
Hz), 130.6, 130.1, 129.1 (br), 128.7 (br), 127.8 (d, JCP = 6.2 Hz),
127.4, 127.1, 126.7 (d, JCP = 41.5 Hz), 48.2, 47.4 (d, JCP = 47.7 Hz),
45.5, 38.1 (d, JCP = 21.9 Hz), 31.0 (d, JCP = 6.5 Hz), 14.1, 12.0. 31P
NMR (120 MHz, CD2Cl2): δ 65.7 ppm. Anal. Calcd (found) for
C32H44AuF6NPSb: C, 42.40 (42.42); H, 4.89 (4.85); N, 1.55 (1.47).
[(t-Bu)2(o-biphen−yl)PAu][1,3-dimethyl-2-methylene-2,3-dihydro-
1H-imidazole]+SbF6 (6). Complex 6 was prepared according to the
procedure to prepare 1. The product was obtained as an off-white solid
(65 mg, 74% yield). The complex was recrystallized from CH2Cl2/
Et2O at −20 °C.
1H NMR (300 MHz, CD2Cl2): δ 7.87 (m, 1H), 7.58−7.36 (m, 5H),
7.29−7.13 (m, 3H), 6.76 (s, 2H), 3.45 (s, 6H), 1.42 (d, JHP = 9 Hz,
2H), 1.31 (d, JHP = 15 Hz, 18H). 13C NMR (125 MHz, CD2Cl2): δ
157.7 (d, J = 4.7 Hz), 149.8 (d, J = 15.3 Hz), 144.2 (d, J = 5.9 Hz),
135.1 (s), 133.4 (d, J = 7.7 Hz), 131.0 (d, J = 2.2 Hz), 130.3 (s), 128.7
(s), 127.6 (d, J = 36.7 Hz), 127.6 (d, J = 6 Hz), 127.4 (s), 119.0 (s),
38.1 (d, J = 21.3 Hz), 34.4 (s), 31.0 (d, J = 6.6 Hz), 21.9 (d, J = 74
Hz). Anal. Calcd (found) for C26H37AuF6N2PSb: C, 37.12 (36.99); H,
4.43 (4.66); N, 3.33 (3.32). 31P{1H} NMR (202.5 MHz, CD2Cl2): δ
65.7.
−
[(t-Bu)2(o-biphenyl)PAu][2-methylene-1-phenylpyrrolidine]+SbF6
(3). (t-Bu)2(o-biphenyl)phosphine chloride (65.80 mg, 0.124 mmol)
and NaSbF6 (32.01 mg, 0.124 mmol) were placed in a flask and
dissolved in THF (4 mL). The solution was stirred briefly, and N-
(pent-3-yn-1-yl)aniline (39.40 mg, 0.247 mmol) was added to the
solution. The solution was stirred for 1 h under argon and then filtered
through Celite and triturated in ethyl ether to yield a white powder.
The product was recrystallized at −20 °C by dissolution in CH2Cl2/
hexanes to give colorless crystals (44.8 mg, 41% yield).
ASSOCIATED CONTENT
* Supporting Information
■
1H NMR (300 MHz, CD2Cl2): δ 7.91−7.86 (m, 1H), 7.63−7.45
(m, 5H), 7.33−7.10 (m, 6H), 7.06 (d, J = 3.6 Hz, 2H), 4.12 (t, J = 6.6
Hz, 2H), 3.15 (t, J = 7.8 Hz, 2H), 2.22 (pentet, J = 7.5, 2H), 1.85 (d,
JHP =8.5 Hz, 2H), 1.39 (d, JHP = 15.3 Hz, 18H). 13C NMR (125 MHz,
CD2Cl2): δ 189.9 (d, J = 3.5 Hz), 149.7 (d, J = 15.3 Hz), 144.0 (d, J =
6.4 Hz), 138.3(s), 134.8 (d, J = 1.4 Hz), 133.6 (d, J = 7.2), 131.5 (d, J
= 1.9 Hz), 130.8 (s), 130.2 (s), 130.1 (s), 129.0 (s), 128.0 (d, J = 6.2
Hz), 127.6 (s), 126.7 (d, J=41.1 Hz), 125.4 (s), 60.1 (s), 39.5 (d, J =
49.6 Hz), 38.6 (s), 38.2 (d, J = 21.4), 31.2 (d, J = 6.6 Hz), 21.21 (s).
31P{1H} NMR (202.5 MHz, CD2Cl2): δ 65.9. Anal. Calcd (found) for
C31H40AuF6NPSb: C, 41.82 (41.76); H, 4.53 (4.59); N, 1.57 (1.55).
[(t-Bu)2(o-biphenyl)PAu][N,N-diethyl-1-phenylprop-1-en-1-ami-
S
Text, tables, figures, and CIF files giving characterization data
and isolation details for free enamines, gold enamines with the
t-Bu3P and Ph3P ligands, and gold amines, experimental details
regarding equilibrium binding studies and DNMR simulation of
2, full details of analysis and crystallographic data for all crystal
structures (1, 3−6). This material is available free of charge via
AUTHOR INFORMATION
Corresponding Author
■
ne]+SbF6−(4). In
a glovebox, [(t-Bu)2(o-biphenyl)PAu]-
−
[acetonitrile]+SbF6 (36.7 mg, 0.47 mmol) was weighed into a
flame-dried 10 mL round-bottomed flask equipped with a stir bar.
Anhydrous CH2Cl2 (2 mL) was added, and the flask was capped with a
septum. The reaction flask was then transferred into a fume hood and
cooled to −78 °C using an acetone/dry ice bath. N,N-Diethyl-1-
phenylprop-1-en-1-amine (10.4 μL, 0.5 mmol) was added, and the
reaction mixture was stirred at −60 °C for 10 min under argon. The
cooling bath was removed, and the solvents were removed in vacuo.
The crude product was triturated with hexanes (2×) and dried under
vacuum. The product was obtained as an off-white solid (45 mg, 98%
yield). The product was recrystallized with CH2Cl2/Et2O at −20 °C.
1H NMR (300 MHz, CD2Cl2): δ 7.96−7.90 (m, 1H), 7.60−7.40
(m, 9H), 7.3−7.2 (m, 2H), 7.04−6.98 (m, 2H), 3.47−3.11 (m, 4H),
1.95 (dq, JHP = 9.5, JHH = 5.7 Hz, 1H), 1.46 (d, JHP = 15.5 Hz, 9H),
1.39 (d, JHP = 15.5 Hz, 9H), 1.38 (hidden t, 3H), 0.99 (t, J = 7.1 Hz,
3H), 0.96 (dd, JHH = 5.7, JHP = 2.8 Hz, 3H). 13C NMR (125 MHz,
CD2Cl2): δ 187.1 ppm (d, J = 3.3 Hz), 149.5 (d, J = 15.2 Hz), 144.9
Author Contributions
†Madhavi Sriram and Yuyang Zhu share equal authorship.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Acknowledgement is made to Wake Forest University for
startup funds. We thank Dr. Marcus Wright for assistance in the
NMR facility. We wish to acknowledge the National Science
Foundation for the funding of the purchase of the X-ray
equipment (Award No. 0234489). We also thank Ellen M.
Petryna for preparation and characterization of {[(t-Bu)2(o-
biphenyl)P]Au(NEt3)}+SbF6 and Justin K. Piedad for
−
assistance with enamine syntheses.
4163
dx.doi.org/10.1021/om500670z | Organometallics 2014, 33, 4157−4164