M. Reyes-Lezama et al. / Journal of Organometallic Chemistry 693 (2008) 987–995
989
Compound 3: 83% yield, m.p. 112–115 °C. Anal. Calc.
for C43H36O5P2S2Mn2: C, 59.45; H, 4.71. Found: C,
58.69; H, 4.48%. 1H NMR (CDCl3, 300 MHz): d/ppm:
7.27 [m, SPh, PPh2]; 2.17 [s br, PMe]. 31P{1H} NMR
(CDCl3, 121.7 MHz): d/ppm: 49.0 s. 13C{1H} NMR
(CDCl3, 75.6 MHz): d/ppm: 138.14 [s, Ci, SPh]; 134.05 [s,
Co, SPh]; 127.58 [s, Cm, SPh]; 126.62 [s, Cp, SPh]; 136.56
[d, Ci, 1JPC = 40.5 Hz, PPh2]; 131.94 [d, Cm, 2JPC = 9.0 Hz,
was dissolved in 20 mL of dichloromethane and filtered.
The solvent was eliminated under reduced pressure leaving
behind 6 and 7 as purple powders.
Compound 6: 62% yield, m.p. 97–101 °C. 1H NMR
(CDCl3, 300 MHz): d/ppm: 7.39 [m, 30H, PPh3]; 6.79 [s,
2H, Hm, m-H2NC6H4S–]; 6.46 [s, 2H, Ho, m-H2NC6H4-
0
S–]; 6.15 [s, 2H, Ho , m-H2NC6H4S–]; 6.00 [s, 2H, Hp, m-
H2NC6H4S–]; 3.66, 3.43 [s, 4H, –NH2]. 31P{1H} NMR
(CDCl3, 121.7 MHz): d/ppm: 66.0 s. 13C{1H} NMR
(CDCl3, 75.6 MHz): d/ppm: 249.14 [s, (l-CO)]; 222.15 [d,
1
PPh2]; 129.47 [s, Cp, PPh3]; 18.53 [d, JPC = 30.0 Hz, Me].
MS (m/e): 868 [M]+.
2
Compound 4: 82% yield, m.p. 115–120 °C. Anal. Calc.
for C23H28O11P2S2Mn2: C, 38.55; H, 3.91. Found: C,
37.86; H, 4.06%. 1H NMR (CDCl3, 300 MHz): d/ppm:
7.4 [m, 4H, Ho, SPh]; 7.1 [m, 6H, HmHp, SPh]; 3.63 [br s,
18H, P(OMe)3]. 31P{1H} NMR (CDCl3, 121.7 MHz):
d/ppm: 181.0 s. 13C{1H} NMR (CDCl3, 75.6 MHz):
d/ppm: 138.34 [s, Ci, SPh]; 133.60 [s, Co, SPh]; 127.99 [s,
Cm, SPh]; 126.89 [s, Cp, SPh]; 52.82 [s br, P(OMe)3]. MS
(m/e): 716 [M]+.
CO, JC–P = 23.6 Hz]; 145.36 [s, Ci(N), m-H2NC6H4S–];
138.97 [s, Ci(S), m-H2NC6H4S–]; 137.24 [d, Ci, PPh3,
2
JCi–P = 10.9 Hz]; 133.90 [d, Co, PPh3, JCo–P = 8.6 Hz];
130.78 [s, Co, m-H2NC6H4S–]; 129.48 [s, Cp, PPh3];
3
128.88 [d, Cm, PPh3, JCm–P = 8.6 Hz]; 124.75 [s, Cp, m-
0
H2NC6H4S–]; 121.06 [s, Co , m-H2NC6H4S–]; 113.6 [s,
Cm, m-H2NC6H4S–]. MS (m/e): 967 [Mꢀ2CO]+.
1
Compound 7: 63% yield, m.p. 112–115 °C. H NMR
(CDCl3, 300 MHz): d/ppm: 7.39 [m, 30H, PPh3]; 6.55 [d,
3
Compound 5: 80% yield, m.p. 115–118 °C. Anal. Calc.
for C29H40O11P2S2Mn2: C, 41.75; H, 5.15. Found: C,
41.89; H, 5.01%. 1H NMR (CDCl3, 300 MHz): d/ppm:
7.4 [m, 4H, Ho, SPh]; 7.1 [m, 6H, HmHp, SPh]; 3.98 [q,
4H, Hm, JH Hm = 9.1 Hz, p-H2NC6H4S–]; 6.33 [d, 4H,
o
3
Ho, JH Ho = 9.1 Hz, p-H2NC6H4S–]; 3.6 [s, 4H, –NH2].
m
31P{1H} NMR (CDCl3, 121.7 MHz): d/ppm: 67.0 s.
13C{1H} NMR (CDCl3, 75.6 MHz): d/ppm: 250.11 [s, (l-
3
2
12H, JHH = 7.5 Hz, P(OCH2CH3)3]; 1.23 [t, 18H,
CO)]; 222.15 [d, CO, JC–P = 12.9 Hz]; 145.26 [s, Ci(N),
3JHH = 7.5 Hz, P(OCH2CH3)3]. 31P{1H} NMR (CDCl3,
121.7 MHz): d/ppm: 175.0 s. 13C{1H} NMR (CDCl3,
75.6 MHz): d/ppm: 138.77 [s, Ci, SPh]; 133.62 [s, Co,
SPh]; 127.73 [s, Cm, SPh]; 126.6 [s, Cp, SPh]; 61.56 [s br,
P(OCH2CH3)3]; 16.1 [s br, P(OCH2CH3)3]. MS (m/e): 800
[M]+.
p-H2NC6H4S–]; 136.79 [s, Ci(S), p-H2NC6H4S–]; 135.41
[d, Ci, PPh3, JCi–P = 3.2 Hz]; 133.80 [d, Co, PPh3,
2JCo–P = 9.8 Hz]; 132.10 [s, Co, p-H2NC6H4S–]; 129.36 [s,
3
Cp, PPh3]; 127.84 [d, Cm, PPh3, JCm–P = 7.6 Hz]; 115.42
[s, Cm, p-H2NC6H4S–]. MS (m/e): 1023 [M]+.
2.1.3. Preparation of 8
Equimolar amounts of [g5-(C5H7)Mn(CO)3] (1),
(0.73 mmol, 150 mg) and trimethylphosphine (0.73 mmol,
55 mg) were mixed in 150 mL of fresh distilled cyclohexane
in a 250 mL round bottom flask previously purged with
nitrogen. Phenyl mercaptan (1.46 mmol, 160 mg) was then
added and the mixture was set at reflux temperature. Sam-
ples were collected every 15 min for monitoring purposes
(m(CO) infrared pattern). After 1.5 h the reaction was com-
pleted. The solvent was eliminated under reduced pressure
leaving behind a dark purple powder. The powder was
washed with hexane (3 ꢁ 10 mL). Elimination of the solvent
under reduced pressure afforded 8; 87% yield. Suitable crys-
tals for an X-ray analysis were obtained by diffusion of a
dichloromethane solution of 8 in hexane at 5 °C for 2 weeks.
1
2.1.1. Detection of cis-1,4-pentadiene by H NMR
Complex 1 and PPh3 (1:1 molar ratio) were dissolved in
degassed dry cyclohexane-d12 in an NMR tube purged with
dry nitrogen. Two equivalents of PhSH were added. The
reaction mixture was heated to 60 °C and monitored by
1H NMR in the region 5.5–7 ppm (internal hydrogens of
cis-piperylene) and the signals of 0.52 and 2.56 ppm corre-
sponding to Hanti and Hsyn of 1, respectively. Complete dis-
appearance of the latter and formation of cis-piperylene
occurred within 30 min of reaction.
2.1.2. General procedure for the synthesis of complexes 6 and
7
Equimolar amounts of [g5-(C5H7)Mn(CO)3] (1.5 mmol,
300 mg for 6 and 1.2 mmol, 250 mg for 7) and triphenyl-
phosphine (1.5 mmol, 381 mg and 1.2 mmol, 318 mg, resp.)
were mixed in 150 mL of fresh distilled cyclohexane in a
250 mL round bottom flask previously purged with nitro-
gen. Two equivalents of aminothiophenol (2.9 mmol,
364 mg of m- and 2.4 mmol, 303 mg of p-aminothiophenol)
were then added and the mixture was set at reflux temper-
ature. Samples were collected every 15 min for monitoring
purposes. After 2 h for m-aminothiophenol and 2.5 h for
p-aminothiophenol the reaction was completed. The reac-
tion mixture was passed through a filter to separate the
cyclohexane soluble 1 which did not react. The residue
2.1.4. Alternative preparation of 8
Phenyl mercaptan (0.89 mmol, 98 mg) and [g3-
(C5H7)Mn(PMe3)(CO)3] (0.45 mmol, 126 mg) were
dissolved in 150 mL of cyclohexane in a 250 mL round bot-
tom flask. The reaction mixture was refluxed for 1 h (until
no further changes in the m(CO) region of the IR spectrum
were detected). The purple powder formed was separated
by filtration, washed with hexane (ca. 20 mL) and dried
under vacuum.
1
Compound 8: 96% yield, m.p. 119–121 °C. H NMR
(CDCl3, 300 MHz): d/ppm: 7.33 [s, 2H, Hp, SPh]; 7.24 [s,