10.1002/ejic.201900124
European Journal of Inorganic Chemistry
FULL PAPER
and adsorbed on silica gel in vacuo. Column chromatography was
performed using silica packed as a slurry and CH2Cl2 and n-hexane (2:3)
for elution. The desired product was eluated as a red-brownish band and
the solvent was removed in vacuo. Yield: 62.5 % (362 mg, 0.52 mmol).
The brownish solid was dissolved in a minimal amount of dry THF and
crystallization was achieved after diffusion of dry methanol into the
solution yielding brownish-red prismatic needles.
Synthesis of [Mo(CO)2(dppe)(pydt)] {MoPydt}
[Mo(CO)2(dppe)(pydt)] was prepared as described for the analogous
compound [Mo(CO)2(cydt)(dppe)] with pydt (205.4 mg, 1.18 mmol, 1.1
eq.) ligand instead of cydt. Yield: 52.4 % (391.4 mg, 0.562 mmol).
1H NMR (300 MHz, C4D8O, 25°C): δ = 2.55 (m, 4H, 2*CH2), 2.87 (t, 2H,
CH2), 3.73 (t, 2H, CH2), 4.66 (s, 2H, CH2), 7.00 (m, 4H, 4 CHarom.), 7.20-
7.31 (m, 6H, CHarom.), 7.36-7.43 (m, 6H, CHarom.); 7.46 bis 7.52 (m, 4H,
CHarom.) ppm. 13C NMR (75.5 MHz, C4D8O, 25°C): δ = 28.6 (m, CH2),
36.5 (s, CH2), 65.5 (s, CH2), 73.9 (s, CH2), 128.9 (dt, 2*2 CH, J1 = 32.1
Hz, J2 = 5.2 Hz), 130.8 (d, 2*2 CH, J1 = 31.4 Hz), 133.4 (dt, 2*2 CH, J1 =
1H NMR (300 MHz, C4D8O, 25°C): δ = 1.73 (s, 4H, 2*CH2), 2.51 (m, 4H,
2*CH2), 2.87 (s (br), 4H, 2*CH2), 6.99 (m, 4H, 4 CHarom), 7.02 to 7.53 (m,
16H, CHarom). 13C NMR (75.5 MHz, C4D8O, 25°C): δ = 25.0 (s, CH2), 28.6
(t, J1 = 21.5 Hz, CH2), 36.3 (s, CH2), 128.8 (dt, J1 = 5.0 Hz, J2 = 34.7 Hz,
CH), 130.6 (d, J1 = 33.0 Hz, CH), 133.5 (dt, J1 = 16.9 Hz, J2 = 5.0 Hz,
CH), 136.4 (m, Cquart., arom.), 138.3 (m, Cquart., arom.), 153.3 (t, J1 = 2.2 Hz,
Cquart., C-S), 243.2 (d, CO, J = 14.7 Hz) ppm. 31P NMR (121.5 MHz, C4D8O,
25°C): δ = 82.80 (s) ppm. 135DEPT NMR (75.5 MHz, C4D8O, 25°C): δ =
25.0 (neg., CH2), 28.8 (neg., CH2), 36.5 (neg., CH2), 128.8 (pos., CH),
130.6 (pos., CH), 133.5 (pos., CH) ppm. HH-COSY NMR (300 MHz,
C4D8O, 25°C): δ = 1.71 und 2.87 (2 CH2,cydt with CH2,cydt) ppm. HSQC-
15.3 Hz, J2 = 5.0 Hz), 136.2 (m, Cquart.), 138.0 (m, Cquart.), 150.3 (s, Cquart.
,
C-S), 150.4 (s, Cquart., C-S), 242.8 (d, CO, J = 15.3Hz) ppm. 31P NMR
(121.5 MHz, C4D8O, 25°C): δ = 82.97 (s) ppm. 135DEPT NMR (75.5 MHz,
C4D8O, 25°C): δ = 28.6 (neg., CH2), 36.5 (neg., CH2), 65.5 (neg., CH2),
73.9 (neg., CH2), 128.7 (pos., CH), 129.1 (pos., CH), 130.5 (pos., CH),
130.9 (pos., CH), 133.3 (pos., CH) ppm. HH-COSY NMR (300 MHz,
C4D8O, 25°C): δ = 2.87 and 3.73 (2 CH2,pydt with CH2,pydt), 2.87 and 4.66
(2 CH2,pydt with CH2,pydt) ppm. HSQC NMR (300 and 75.5 MHz, C4D8O,
25°C): δ = 2.55 (1H, 2 CH2,pydt) and 28.6 (13C, CH2, pydt), 2.87 (1H, 2 CH2)
and 36.5 (13C, CH2, dppe), 3.73 (1H, CH2,pydt) and 65.5 (13C, CH2), 4.66 (1H,
CH2,pydt) and 73.9 (13C, CH2), 6.97-7.52 (1H, CHarom.) and 128.7-138.0
DEPT NMR (300 and 75.5 MHz, C4D8O, 25°C): δ = 1.73 (1H,2 CH2,cydt
)
and 25.0 (13C, CH2, cydt), 2.51 (1H, 2 CH2) and 28.8 (13C, CH2, dppe), 2.87
(1H, CH2,cydt) and 36.5 (13C, CH2), 7.02-7.53 (1H, CHarom.) and 128.8-
138.4 (13C, CHarom.) ppm. HMBC NMR (300 and 75.5 MHz, C4D8O,
25°C): δ = 1.73 (1H, CH2,cydt) and 25.0 (13C, CH2), 2.87 (1H, CH2,cydt) and
25.0 (13C, CH2), 1.73 (1H, CH2,cydt) and 153.9 (13C, C-S), 2.87 (1H,
CH2,cydt) and 153.9 (13C, C-S), 7.02-7.53 (1H, CHarom.) and 128.8-138.4
(
13C, CHarom.) ppm. HMBC NMR (300 and 75.5 MHz, C4D8O, 25°C): δ =
2.87 (1H, CH2,pydt) and 65.5 (13C, CH2); 2.87 (1H, CH2,pydt) and 150.3 (13C,
CH2); 3.73 (1H, CH2,pydt) and 73.9 (13C, CH2); 3.73 (1H, CH2,pydt) and 73.9
(
13C, CH2; 3.73 (1H, CH2,pydt) and 150.3 (13C, C-S); 4.66 (1H, CH2,pydt) and
13C, CHarom.) ppm. Rf-value (silica gel): 0.28 (n)-hexane/CH2Cl2: 3/2).
150.3 (13C, C-S); 6.97-7.52 (1H, CHarom.) and 128.9-133.4 (13C, CHarom.).
(
UV-vis: ε in THF (M-1 cm-1) = 6818 (321 nm), 5201 (432 nm). IR (NaCl,
0.04 mm, in THF.) c = 0.035 M): ν = 1300-1700 cm-1, 1874 cm-1, 1938
cm-1, 1949 cm-1. IR (KBr): ν = 1433 cm-1, 1861 cm-1, 1935 cm-1. Calcd for
C34H32O2P2S2Mo: C: 58.79; H: 4.64; S: 9.23. Found: C: 58.34; H: 4.78; S:
9.25.
Rf-value (silica gel): 0.55 (n-hexane/CH2Cl2: 3.5/1.5). UV-vis:
ε in
acetonitrile (M-1 cm-1) = 4281 (425 nm). IR (KBr): ν = 1431 cm-1, 1863 cm-
1, 1929 cm-1. Calcd for C33H30O3P2S2Mo: C: 56.90; H: 4.34; S: 9.20.
Found: C: 56.85; H: 4.78; S: 9.25.
Synthesis of [W(CO)2(dppe)(pydt)] {WPydt}
Synthesis of [W(CO)2(cydt)(dppe)] {WCydt}
[W(CO)2(dppe)(pydt)] was prepared as described for the analogous
compound [W(CO)2(cydt)(dppe)] with pydt ligand (144 mg, 0.827 mmol,
1.1 eq.) instead of cydt. Yield: 34.1 % (198.5 mg, 0.253 mmol).
The
synthesis
followed
the
procedure
described
for
[Mo(CO)2(cydt)(dppe)]; [W(CO)4(dppe)] (900 mg, 1.3 mmol, 1 eq.) and
cydt (307.3 mg, 1.78 mmol, 1.37 eq.) were used. The product crystallized
as dark red prismatic blocks. Yield: 50.5 % (513.4 mg, 0.656 mmol).
1H NMR (300 MHz, C4D8O, 25°C): δ = 2.62 (m, 4H, 2*CH2); 2.81 (t, 2H,
CH2), 3.70 (t, 2H, CH2), 4.62 (s, 2H, CH2), 7.05 (m, 4H, 4 CHarom.), 7.20-
7.31 (m, 6H, CHarom.), 7.34-7.47 (m, 10H, CHarom.) ppm. 13C NMR (75.5
MHz, C4D8O, 25°C): δ = 29.8 (m, CH2), 36.5 (s, CH2), 65.8 (s, CH2), 74.3
(s, CH2), 128.9 (dt, 2*2 CH, J1 = 28.5 Hz, J2 = 5.0 Hz), 130.8 (d, 2*2 CH,
J1 = 28.5 Hz), 133.7 (dt, 2*2 CH, J1 = 17.1 Hz, J2 = 5.0 Hz), 135.8 (d,
Cquart., J1 = 48 Hz), 138.5 (d, Cquart., J1 = 48 Hz), 148.6 (s, Cquart., C-S),
148.7 (s, Cquart., C-S), 234.6 (m, CO) ppm. 31P NMR (121.5 MHz, C4D8O,
25°C): δ = 59.94 (s, Sat.183W: J = 184 Hz) ppm. 135DEPT NMR (75.5 MHz,
C4D8O, 25°C): δ = 29.8 (neg., CH2), 36.5 (neg., CH2), 65.8 (neg., CH2),
74.3 (neg., CH2), 128.7 (pos., CH), 129.1 (pos., CH), 130.6 (pos., CH),
131.0 (pos., CH), 133.6 (pos., CH), 133.8 (pos., CH). HH-COSY NMR
(300 MHz, C4D8O, 25°C): δ = 2.81 (2 CH2,pydt and 3.70 CH2,pydt), 2.81 (2
CH2,pydt and 4.62 CH2,pydt) ppm. HSQC-DEPT NMR (300 and 75.5 MHz,
C4D8O, 25°C): δ = 2.62 (1H, 2 CH2, dppe) and 29.8 (13C, CH2), 2.81 (1H,2
CH2) and 36.5 (13C, CH2), 3.70 (1H, CH2,pydt) and 65.8 (13C, CH2), 4.62
(1H,2 CH2,pydt) and 74.3 (13C, CH2), 7.05-7.47 (1H, CHarom.) and 128.7-
138.5 (13C, CHarom.) ppm. HMBC NMR (300 and 75.5 MHz, C4D8O,
25°C): δ = 2.81 (1H, CH2,pydt) and 148.7 (13C, CH2), 3.70 (1H, CH2,pydt) and
74.3 (13C, CH2), 3.70 (1H, CH2,pydt) and 148.7 (13C, C-S), 4.62 (1H,
CH2,pydt) and 65.8 (13C, CH2), 4.62 (1H, CH2,pydt) and 148.6 (13C, C-S),
7.05-7.47 (1H, CHarom.) and 128.7-138.5 (13C, CHarom.) ppm. Rf-value
(silica gel): 0.57 (n-hexane/CH2Cl2: 4/1). UV-vis: ε in acetonitrile (M-1 cm-
1) = 7975 (296 nm), 4775 (388 nm), 1083 (500 nm). IR (KBr): ν = 1433
cm-1, 1852 cm-1, 1921 cm-1. Calcd for C33H30O3P2S2W: C: 50.52; H: 3.85;
S: 8.17. Found: C: 50.71; H: 3.74; S: 8.16.
1H NMR (300 MHz, C4D8O, 25°C): δ = 1.68 (m, 4H, 2 CH2), 2.59 (s, 4H),
2.79 (m, 4H, 2*CH2), 7.04 (m, 4H, CHarom.), 7.23 (m,6H, CHarom.), 7.40 (m,
10H, CHarom.) ppm. 13C NMR (75.5 MHz, C4D8O, 25°C): δ = 25.2 (s, CH2),
29.8 (m, CH2), 36.2 (s, CH2), 128.8 (dt, J1 = 31.4 Hz, J2 = 5.0 Hz, CH),
130.7 (d, J1 = 30.3 Hz, CH), 133.7 (dt, J1 = 18.7 Hz, J2 = 5.0 Hz, CH),
136.0 (m, Cquart.), 138.7 (m, Cquart.), 150.7 (t, J1 = 2.5 Hz, Cquart.), 235.7 (m,
CO) ppm. 31P NMR (121.5 MHz, C4D8O, 25°C): δ = 61.96 (s, Sat.183W: J =
187.07 Hz) ppm. 135DEPT NMR (75.5 MHz, C4D8O, 25°C): δ = 25.2 (neg.,
CH2), 29.8 (neg., CH2), 36.2 (neg., CH2), 128.8 (pos., CH), 130.7 (pos.,
CH), 133.7 (pos., CH). HH-COSY NMR (300 MHz, C4D8O, 25°C): δ =
1.68 and 2.79 (2 CH2,cydt with CH2,cydt) ppm. HSQC NMR (300 und 75.5
MHz, C4D8O, 25°C): δ = 1.68 (1H,2 CH2,cydt) and 25.2 (13C, CH2, cydt), 2.59
(1H, 2 CH2) and 29.8 (13C, CH2, dppe), 2.79 (1H, CH2,cydt) and 36.1 (C4D8O
13C, CH2), 7.04-7.40 (1H, CHarom.) and 128.6-138.7 (13C, CHarom.) ppm.
HMBC NMR (300 und 75.5 MHz, C4D8O, 25°C): δ = 1.68 (1H, CH2,cydt
)
and 25.2 (13C, CH2), 2.79 (1H, CH2,cydt) and 25.2 (13C, CH2), 1.68 (1H,
CH2,cydt) and 150.7 (13C, C-S), 2.79 (1H, CH2,cydt) and 150.7 (13C, C-S)
ppm. Rf-value (silica gel): 0.24 (n-hexane/CH2Cl2 3:2). UV-vis: ε in THF
(M-1 cm-1) = 3530 (387 nm), 2785 (467 nm). IR (NaCl, 0.04 mm, in dry
THF., c = 0.033 M): ν = 1300-1700 cm-1, 1865 cm-1, 1931 cm-1, 1942 cm-1.
IR (KBr):
ν =
1433 cm-1, 1854 cm-1, 1923 cm-1. Calcd for
C34H32O2P2S2W}: C: 52.19; H: 4.19; S: 8.19. Found: C: 52.12; H: 4.00; S:
7.91.
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