Organometallics
Article
7.80−7.71 (m, 12H; o-C6H5), 7.47 (d, J(H,H) = 8.3 Hz, 2H; m-C6H4),
7.44−7.33 (m, 18H; m,p-C6H5), 6.15 (d, J(H,H) = 8.3 Hz, 2H; o-
C6H4), 2.45 (s, 3H; CH3). 13C NMR (126 MHz, CDCl3, 77.2 ppm): δ
= 197.6 (1C; CO), 135.2 (t, J(C,P) = 6.3 Hz, 12C; o-C6H5), 133.8
(1C; p-C6H4), 132.6 (1C; i-C6H4), 131.6 (t, J(C,P) = 25.0 Hz, 6C; i-
C6H5), 130.7 (2C; o-C6H4), 130.5 (6C; p-C6H5), 128.2 (t, J(C,P) =
5.3 Hz, 12C; m-C6H5), 127.5 (2C; m-C6H4), 110.7 (t, J(C,P) = 6.7 Hz,
1C; PdCC), 106.8 (t, J(C,P) = 14.0 Hz, 1C; PdCC), 26.5 (1C;
CH3). 31P NMR (202 MHz, CDCl3, external H3PO4 0 ppm): δ = 24.9
(s, 2P; PPh3). HRMS(ESI): m/z calcd for C46H37OP2Pd 773.1366 [M
− Br]+; found 773.1367. IR (Nujol mull; cm−1): ν = 2116 (CC),
1679 cm−1 (CO).
(0.050 g, 2.0 mmol), and DCM (10 mL) were reacted according to the
general procedure. Yield: 0.144 g (82%, 0.163 mmol). Decomposition:
208 °C. 1H NMR (500 MHz, CDCl3, 7.26 ppm): δ = 8.05 (d, J(H,H)
= 9.0 Hz, 2H; o-C6H4), 7.76−7.69 (m, 12H; o-C6H5), 7.47−7.36 (m,
18H; m,p-C6H5), 7.27 (d, J(H,H) = 9.0 Hz, 2H; m-C6H4). 13C NMR
(151 MHz, CDCl3, 77.2 ppm): δ = 146.4 (1C; p-C6H5), 135.2 (t,
J(C,P) = 6.2 Hz, 12C; o-C6H5), 132.7 (2C; o-C6H5), 131.6 (1C; i-
C6H5), 131.0 (t, J(C,P) = 25.2 Hz, 6C; i-C6H5), 130.7 (6C; p-C6H5),
128.3 (t, J(C,P) = 5.4 Hz, 12C; m-C6H5), 123.6 (2C; m-C6H5), 108.7
(t, J(C,P) = 14.5 Hz, 1C; PdCCCC), 92.1 (t, J(C,P) = 6.8 Hz,
1C; PdCCCC), 83.4 (1C; PdCCCC), 69.8 (1C; PdC
CCC). 31P NMR (202 MHz, CDCl3, external H3PO4 0 ppm): δ =
24.4 (s, 2P; PPh3). HRMS(ESI): m/z calcd for C46H34NO2P2Pd
800.1111 [M − Br−]+; found 800.1113. IR (Nujol mull; cm−1): ν =
2187 (CC), 2072 (CC), 1514 (NO2), 1338 (NO2).
Bromo((4-formylphenyl)ethynyl)bis(triphenylphosphine)-
palladium, trans-[PdBr(PPh3)2(CCC6H4C(O)H)] (4-C2[Pd]Br).
Pd(PPh3)4 (0.216 g, 0.187 mmol), 4-(bromoethynyl)benzaldehyde
(0.039 g, 0.19 mmol), and DCM (10 mL) were reacted according to
the general procedure. Yield: 0.094 g (59%, 0.11 mmol). Mp with
decomposition: 102 °C. 1H NMR (500 MHz, CDCl3, 7.26 ppm): δ =
9.78 (s, 1H; CHO), 7.82−7.65 (m, 12H; o-C6H5), 7.45−7.31 (m,
Bromo((4-acetylphenyl)butadiynyl)bis(triphenylphosphine)-
palladium, trans-[PdBr(PPh3)2((CC)2C6H4C(O)CH3)] (3-
C4[Pd]Br). Pd(PPh3)4 (0.110 g, 0.095 mmol), 4-(bromobutadiynyl)-
acetophenone (0.025 g, 0.10 mmol), and DCM (10 mL) were reacted
according to the general procedure. Yield: 0.073 g (87%, 0.083 mmol).
Decomposition: 198 °C. 1H NMR (600 MHz, CDCl3, 7.26 ppm): δ =
7.78 (d, J(H,H) = 8.8 Hz, 2H; m-C6H4), 7.75−7.71 (m, 12H; o-C6H5),
7.45−7.37 (m, 18H; m,p-C6H5), 7.24 (d, J(H,H) = 8.8 Hz, 2H; o-
C6H4), 2.54 (s, 3H; CH3). 13C NMR (151 MHz, CDCl3, 77.2 ppm): δ
= 191.4 (1C; C(O)CH3), 135.6 (1C; C6H4), 135.2 (t, J(C,P) = 6.3
Hz, 12C; o-C6H5), 132.2 (2C; C6H4), 131.1 (t, J(C,P) = 25.0 Hz, 6C;
i-C6H5), 130.7 (6C; p-C6H5), 129.4 (1C; C6H4), 128.2 (t, J(C,P) = 5.4
Hz, 12C; m-C6H5), 128.1 (2C; C6H4), 105.9 (t, J(C,P) = 14.5 Hz, 1C;
PdCCCC), 92.4 (t, J(C,P) = 7.0 Hz, 1C; PdCCCC), 81.2
20H; m,p-C6H5, m-C6H4), 6.21 (d, J(H,H) = 8.0 Hz, 2H; o-C6H4). 13
C
NMR (126 MHz, CDCl3, 77.2 ppm): δ = 191.7 (1C; CHO), 135.2 (t,
J(C,P) = 6.3 Hz, 12C; o-C6H5), 134.0 (1C; i-C6H4), 133.2 (1C; p-
C6H4), 131.5 (t, J(C,P) = 25.0 Hz, 6C; i-C6H5), 131.1 (2C; o-C6H4),
130.6 (6C; p-C6H5), 128.9 (2C; m-C6H4), 128.2 (t, J(C,P) = 5.3 Hz,
12C; m-C6H5), 110.8 (d, J(C,P) = 6.7 Hz, 1C; PdCC), 108.8 (1C;
PdCC). 31P NMR (202 MHz, CDCl3, external H3PO4 0 ppm): δ =
25.0 (s, 2P; PPh3). HRMS(ESI): m/z calcd for C45H35OP2Pd
759.1209 [M − Br]+; found 759.1199. IR (Nujol mull; cm−1): ν =
2111 (CC), 1693 (CO).
(1C; PdCCCC), 70.8 (1C; PdCCCC), 26.7 (1C; CH3). 31
P
Bromo((4-benzoylphenyl)ethynyl)bis(triphenylphosphine)-
palladium, trans-[PdBr(PPh3)2(CCC6H4C(O)C6H5)] (5-
C2[Pd]Br). Pd(PPh3)4 (0.197 g, 0.170 mmol), 4-(bromoethynyl)-
benzophenone (0.049 g, 0.17 mmol), and DCM (10 mL) were reacted
according to the general procedure. Yield: 0.117 g (75%, 0.128 mmol).
Decomposition: 177 °C. 1H NMR (500 MHz, CDCl3, 7.26 ppm): δ =
7.82−7.69 (m, 12H; o-PC6H5), 7.67−7.64 (m, 2H; o-C6H5), 7.56−
7.51 (m, 1H; p-C6H5), 7.46−7.33 (m, 22H; m,p-PC6H5, m-C6H5, m-
C6H4), 6.17 (d, J(H,H) = 8.2 Hz, 2H; o-C6H4). 13C NMR (126 MHz,
CDCl3, 77.2 ppm): δ = 196.3 (1C; CO), 138.2 (1C; i-C6H5), 135.2 (t,
J(C,P) = 6.3 Hz, 12C; o-PC6H5), 134.0 (1C; p-C6H4), 132.1 (1C; p-
C6H5), 131.6 (t, J(C,P) = 25.1 Hz, 6C; i-PC6H5), 130.5 (6C; p-
PC6H5), 130.4 (2C; o-C6H4), 129.9 (2C; o-C6H5), 129.6 (2C; m-
C6H4), 128.6 (1C; i-C6H4), 128.3 (2C; m-C6H5), 128.2 (t, J(C,P) =
5.3 Hz, 12C; m-PC6H5), 110.8 (t, J(C,P) = 6.8 Hz, 1C; PdCC),
108.8 (t, J(C,P) = 14.3 Hz, 1C; PdCC). 31P NMR (203 MHz,
CDCl3, external H3PO4 0 ppm): δ = 25.0 (s, 2P; PPh3). HRMS(ESI):
m/z calcd for C51H39OP2Pd 835.1523 [M − Br]+; found 835.1518. IR
(Nujol mull; cm−1): ν = 2114 (CC), 1657 (CO).
NMR (202 MHz, CDCl3, external H3PO4 0 ppm): δ = 24.3 (s, 2P;
PPh3). HRMS(ESI): m/z calcd for C48H37OP2Pd 797.1366 [M −
Br]+; found 797.1352. IR (Nujol mull; cm−1): ν = 2184 (CC), 2069
(CC), 1683 (CO).
B r o m o ( ( 4 - f o r m y l p h e n y l ) b u t a d i y n y l ) b i s -
(triphenylphosphine)palladium, trans-[PdBr(PPh3)2((C
C)2C6H4C(O)H)] (4-C4[Pd]Br). Pd(PPh3)4 (0.120 g, 0.104 mmol), 4-
(bromobutadiynyl)benzaldehyde (0.025 g, 0.107 mmol), and DCM
(10 mL) were reacted according to the general procedure. Yield: 0.089
1
g (96%, 0.10 mmol). Decomposition: 198 °C. H NMR (500 MHz,
CDCl3, 7.26 ppm): δ = 9.93 (s, 1H; CHO), 7.76−7.68 (m, 14H; o-
C6H5, m-C6H4), 7.46−7.37 (m, 18H; m,p-C6H5), 7.30 (d, J(H,H) =
8.1 Hz, 2H; o-C6H4). 13C NMR (partial, 126 MHz, CDCl3, 77.2 ppm):
δ = 191.5 (1C; CO), 135.2 (t, J(C,P) = 6.3 Hz, 12C; o-C6H5), 134.8
(1C; C6H4), 132.6 (2C; C6H4), 131.1 (t, J(C,P) = 25.0 Hz, 6C; i-
C6H5), 130.7 (6C; p-C6H5), 129.5 (2C; C6H4), 128.3 (t, J(C,P) = 5.4
Hz, 12C; m-C6H5), 107.0 (t, J(C,P) = 14.4 Hz, 1C; PdCCCC),
92.4 (t, J(C,P) = 6.4 Hz, 1C; PdCCCC), 82.1 (1C; PdCCC
C), 70.8 (1C; PdCCCC). 31P NMR (121 MHz, CDCl3, external
H3PO4 0 ppm): δ = 24.3 (s, 2P; PPh3). HRMS(ESI): m/z calcd for
C47H35OP2Pd 783.1209 [M − Br]+; found 783.1197. IR (Nujol mull;
cm−1): ν = 2184 (CC), 2069 (CC), 1702 (CO).
Bromo((4-cyanophenyl)butadiynyl)bis(triphenylphosphine)-
palladium, trans-[PdBr(PPh3)2((CC)2C6H4CN)] (1-C4[Pd]Br).
Pd(PPh3)4 (0.225 g, 0.195 mmol), 4-(bromobutadiynyl)benzonitrile
(0.045 g, 0.196 mmol), and DCM (15 mL) were reacted according to
the general procedure. Yield: 0.157 g (93%, 0.182 mmol).
B r o m o ( ( 4 - b e n z o y l p h e n y l ) b u t a d i y n y l ) b i s -
(triphenylphosphine)palladium, trans-[PdBr(PPh3)2((C
C)2C6H4C(O)C6H5)] (5-C4[Pd]Br). Pd(PPh3)4 (0.185 g, 0.160
mmol), 4-(bromobutadiynyl)acetophenone (0.055 g, 0.178 mmol),
and DCM (10 mL) were reacted according to the general procedure.
Yield: 0.128 g (85%, 0.136 mmol). Decomposition: 156 °C. 1H NMR
(600 MHz, CDCl3, 7.26 ppm): δ = 7.76−7.70 (m, 14H; o-PC6H5, o-
C6H5), 7.65 (d, J(H,H) = 8.6 Hz, 2H; m-C6H4), 7.59−7.55 (m, 1H; p-
C6H5), 7.48−7.39 (m, 20H; m,p-PC6H5, m-C6H5), 7.27 (d, J(H,H) =
8.6 Hz, 2H; o-C6H4). 13C NMR (151 MHz, CDCl3, 77.2 ppm): δ =
196.0 (1C; CO), 137.8 (1C; p-C6H4), 136.0 (1C; i-C6H5), 135.2 (t,
J(C,P) = 6.3 Hz, 12C; o-PC6H5), 132.6 (1C; p-C6H5), 131.9 (2C; o-
C6H4), 131.1 (t, J(C,P) = 25.0 Hz, 6C; i-PC6H5), 130.7 (6C; p-
PC6H5), 130.1 (2C; m-C6H4), 130.0 (2C; o-C6H5), 128.8 (2C; i-
C6H4), 128.5 (1C; m-C6H5), 128.3 (t, J(C,P) = 5.3 Hz, 12C; m-
PC6H5), 105.7 (t, J(C,P) = 14.5 Hz, 1C; PdCCCC), 92.5 (t,
J(C,P) = 6.8 Hz, 1C; PdCCCC), 81.0 (1C; PdCCCC), 70.9
(1C; PdCCCC). 31P NMR (121 MHz, CDCl3, external H3PO4 0
1
Decomposition: 206 °C. H NMR (500 MHz, CDCl3, 7.26 ppm): δ
= 7.75−7.69 (m, 12H; o-C6H5), 7.46 (d, J(H,H) = 8.6 Hz, 2H; m-
C6H4), 7.44−7.37 (m, 18H; m,p-C6H5), 7.22 (d, J(H,H) = 8.6 Hz, 2H;
o-C6H4). 13C NMR (151 MHz, CDCl3, 77.2 ppm): δ = 135.2 (t,
J(C,P) = 6.3 Hz, 12C; o-C6H5), 132.5 (2C; m-C6H4), 131.9 (2C; o-
C6H4), 131.0 (t, J(C,P) = 25.0 Hz, 6C; i-C6H5), 130.7 (6C; p-C6H5),
129.4 (1C; i-C6H4), 128.3 (t, J(C,P) = 5.3 Hz, 12C; m-C6H5), 118.9
(1C; CN), 110.5 (1C; p-C6H4), 107.4 (t, J(C,P) = 14.5 Hz, 1C;
PdCCCC), 92.1 (t, J(C,P) = 7.0 Hz, 1C; PdCCCC), 82.2
(1C; PdCCCC), 69.8 (1C; PdCCCC). 31P NMR (121
MHz, CDCl3, external H3PO4 0 ppm): δ = 24.3 (s, 2P; PPh3).
HRMS(ESI): m/z calcd for C47H34NP2Pd 780.1213 [M − Br]+; found
780.1202. IR (Nujol mull; cm−1): ν = 2225 (CN), 2187 (CC),
2065 (CC).
Bromo((4-nitrophenyl)butadiynyl)bis(triphenylphosphine)-
palladium, trans-[PdBr(PPh3)2((CC)2C6H4NO2)] (2-C4[Pd]Br).
Pd(PPh3)4 (0.230 g, 0.199 mmol), 4-(bromobutadiynyl)nitrobenzene
H
Organometallics XXXX, XXX, XXX−XXX