M. Enders et al. / Journal of Organometallic Chemistry 622 (2001) 66–73
71
solution of 685 mg (5.0 mmol) of ZnCl2 in 25 ml THF
was added via cannula and the resulting solution of
(C5H4ZnCl)Mn(CO)3 was stirred for an additional
hour. A solution of (PPh3)2Pd (prepared from 175 mg
(0.25 mmol) of (PPh3)2PdCl2 and 0.50 mmol of Dibal-H
as described above) was added to the yellow solution of
(C5H4ZnCl)Mn(CO)3 via cannula. A total of 1.04 g (5.0
mmol) of 8-bromoquinoline was added dropwise and
the dark solution was allowed to warm to r.t. and
stirred for 5 days. The reaction mixture was quenched
by adding a solution of 10 g (0.25 mol) of NaOH in 50
ml water. After 1.5 h of stirring the organic layer was
separated from the water fraction, which was extracted
twice with THF. The combined organic fractions were
dried over MgSO4, filtered, and evaporated. Column
chromatography on Al2O3/5% H2O using toluene as
eluent yielded 1.49 g (4.50 mmol, 92%) of 5 as a yellow,
lightsensitive solid. IR (toluene): w˜(CO)=1934 (s), 2018
(s) cm−1. 1H-NMR (CDCl3): l=4.88 (pt, 2H, Cp CH);
(pt, 2H, Cp CH); 6.39 (pt, 2H, Cp CH); 7.44 (dd,
3
3J(H3, H2)=4.2 Hz, J(H3, H4)=8.3 Hz, 1H, H3); 7.50
3
3
(dd, J(H, H)=7.2 Hz, J(H, H)=8.1 Hz, 1H, H6);
7.78 (dd, J(H, H)=8.2 Hz, J(H, H)=1.4 Hz, 1H, H5
3
4
or H7); 7.86 (dd, J(H, H)=7.2 Hz, J(H, H)=1.4 Hz,
3
3
1H, H5 or H7); 8.16 (dd, J(H4, H3)=8.3 Hz, J(H4,
3
3
H2)=1.8 Hz, 1H, H4); 8.98 (dd, J(H2, H3)=4.2 Hz,
3
3J(H2, H4)=1.8 Hz, 1H, H2). 13C {1H}-NMR (CDCl3):
l=83.3, 88.3, (CHCp); 103.5 (quart. CCp); 121.3, 126.0,
128.4, 129.2, 136.3, 149.9 (CHquinoline); 128.6, 130.8,
145.4 (quart. Cquinoline); 194.7 (CO). MS (EI), m/z (%):
463 (10) [M+]; 435 (73) [M+−CO]; 407 (100) [M+−2
CO]; 379 (72) [M+−3 CO]; 353 (30); 189.5 (15) [M2+
−3 CO]. C17H10NO3Re (462.48): Calc. C 44.06; H
2.18; N 3.02; Found C 44.47; H 2.56; N 3.07.
4.6. Dicarbonyl[p5-(8-quinolyl)cyclopentadienyl]-
manganese(I) (7)
3
5.86 (pt, 2H, Cp CH); 7.44 (dd, J(H3, H2)=4.1 Hz,
3
3J(H3, H4)=8.3 Hz, 1H, H3); 7.52 (dd, J(H, H)=7.4
A total of 210 mg (0.63 mmol) of tricarbonyl[h5-(8-
chinolyl)cyclopentadienyl]manganese(I) (5) was dis-
solved in a mixture of 25 ml of hexane and 25 ml of
toluene. The yellow solution was irridiated for 4 h in
which the colour changed to dark blue. The solution
was concentrated in vacuum and purified by column
chromatography on Al2O3/5% H2O using toluene as
eluent. Removal of the solvent yielded 186 mg (0.61
mmol, 97%) of 7 as a brown–red powder, m.p. 220°C.
3
3
Hz, J(H, H)=8.1 Hz, 1H, H6); 7.77 (dd, J(H, H)=
8.2 Hz, J(H, H)=1.4 Hz, 1H, H5 or H7); 7.87 (dd,
4
3J(H, H)=7.3 Hz, J(H, H)=1.5 Hz, 1H, H5 or H7);
3
8.17 (dd, J(H4, H3)=8.3 Hz, J(H4, H2)=1.8 Hz, 1H,
H4); 8.98 (dd, 3J(H2, H3)=4.1 Hz, 3J(H2, H4)=1.8 Hz,
1H, H2). 13C {1H}-NMR (CDCl3, 50 MHz) l=81.5,
86.7 (CHCp); 99.5 (quart. CCp); 121.2, 125.9, 128.1,
128.7, 136.3, 149.5 (CHquinoline); 128.6, 131.5, 145.7
(quart. Cquinoline); 225.3 (CO). MS (EI), m/z (%): 331
(0.4) [M+]; 303 (21) [M+−CO]; 247 (100) [M+−3
CO]; 191 (27) [M+−Mn–3 CO–H]; 123.5 (14) [M2+
−3 CO], 55 (42) [Mn+]. C17H10NO3Mn (331.21): Calc.
C 61.65, H 3.04, N 4.23; Found C 61.91, H 3.44, N
4.00.
3
3
IR (toluene): w˜(CO)=1864 (s), 1928 (s) cm−1
.
1H-
NMR (CDCl3): l=3.98 (pt, 2H, Cp CH); 5.59 (pt, 2H,
3
3
Cp CH); 6.94 (dd, J(H3, H2)=5.2 Hz, J(H3, H4)=
8.4 Hz, 1H, H3); 7.48 (dd, J(H, H)=6.9 Hz, J(H,
H)=8.1 Hz, 1H, H6); 7.60 (dd, 3J(H, H)=8.1 Hz,
4J(H, H)=1.4 Hz, 1H, H5 or H7); 7.73 (dd, 3J(H,
3
3
H)=6.8 Hz, J(H, H)=1.4 Hz, 1H, H5 or H7); 7.80
3
4.5. Tricarbonyl[p5-(8-quinolyl)cyclopentadienyl]-
rhenium(I) (6)
(dd, J(H4, H3)=8.4 Hz, J(H4, H2)=1.2 Hz, 1H, H4);
3
3
8.58 (dd, J(H2, H3)=5.2 Hz, J(H2, H4)=1.2 Hz, 1H,
H2). 13C {1H}-NMR (CDCl3): l=78.2, 83.2 (CHCp);
117.3 (quart. CCp); 121.6, 127.1 (2C), 128.3, 134.4, 157.4
(CHquinoline); 128.1, 134.7, 158.6 (quart. Cquinoline); 234.8
(CO). MS (EI), m/z (%): 303 (10) [M+]; 247 (100)
[M+−2 CO]; 191 (15) [CpQ+ −H]; 55 (29) [Mn+].
C16H10NO2Mn (303.20): Calc. C 63.38; H 3.32; N 4.62;
Found C 63.59; H 3.56; N 4.56.
3
3
The procedure is analogous to that for 5 except that
protection against light is not necessary. Scale: 1.2 g
(3.6 mmol) of tricarbonylcyclopentadienylrhenium(I),
1.6 ml (4.0 mmol) of a 2.5 M solution of n-BuLi in
hexane, 0.5 g (3.7 mmol) of ZnCl2, 140 mg (0.2 mmol)
of (PPh3)2PdCl2, 0.4 mmol of Dibal-H, 0.75 g (3.6
mmol) of 8-bromoquinoline.
The reaction mixture was quenched with 8 g (0.2
mol) of NaOH in 40 ml water, the water fraction was
extracted twice with CH2Cl2. The combined organic
layers were dried over MgSO4, concentrated and
filtered over Al2O3/5% H2O. Unreacted CpRe(CO)3 was
removed by sublimation at 100°C and 10−2 mbar.
Column chromatography on Al2O3/5% H2O using tolu-
ene as eluent yielded 1.29 g (2.79 mmol, 78%) of 6 as a
pale yellow solid, m.p. 97°C. IR (toluene): w˜(CO)=
4.7. Dicarbonyl[p5-(8-quinolyl)cyclopentadienyl]-
rhenium(I) (8)
In a quartz-Schlenktube 110 mg (0.25 mmol) of
tricarbonyl[h5 - (8 - chinolyl)cyclopentadienyl]rhenium(I)
(6) were dissolved in 2 ml of toluene. To this mixture 60
ml of hexane were added and the resulting colourless
solution was irradiated for 5 days (150 W high-pressure
mercury lamp). The colour turned to red and small red
1
1926 (s), 2021 (s) cm−1. H-NMR (CDCl3): l=5.47