136
O. Sánchez-Guadarrama et al. / Journal of Organometallic Chemistry 706-707 (2012) 135e139
2
2.1. General procedures
PMe3], 1.66 [d, HMe, PMe3, JPH ¼ 8 Hz]. 13C{1H} NMR (CDCl3,
75.6 MHz): d/ppm: 139.6e136.6 [m, Ci (PNP)]; 131.51e131.35 [m, Co
2.1.1. Route A
(PNP)], 130.5 [s, Cp (PNP)], 128.3e127.9 [m, Cm (PNP)], 15.7 [d, CMe
PMe3, JC-P ¼ 30 Hz], 190.5 [s, broad, CO], 190.4 [s, broad, CO], 189.7
[s, broad, CO]. 31P{1H} NMR (CDCl3, 121.7 MHz):
/ppm: 40.3 [d,
(PNP) JPNP-PMe3 ¼ 22.3 Hz], ꢁ37.1 [t, (PPh3) JPMe3-PNP ¼ 22.3 Hz].
MS (m/e): 796 [M]þ, 739 [M-2CO]þ, 711 [M-3CO]þ, 635 [M-3CO,
PMe3]þ.
,
Synthesis
PR3 ¼ PPh3 (1), PMePh2 (2), PMe2Ph (3), and PMe3 (4). 0.46 g
(0.62 mmol) of [Re(CO)4{Ph2(S)NP(S)Ph2-
2S}] (a) were added to
of
[Re(CO)3(PR3){Ph2P(S)NP(S)Ph2-
k
2S}]
for
d
3
3
k
a 100 mL round bottom flask with stirring containing 30 mL of dry
toluene. An equimolar amount of the corresponding phosphine
(PPh3 0.161 g, PMePh2 0.123 g, PMe2Ph 0.085 g, and PMe3 0.047 g)
was dissolved in 50 mL of toluene and transferred via cannula to the
reaction flask and set to reflux temperature. At the end of the
reaction (detected by 31P NMR monitoring: 60 min for (1), 40 min
for (2), 30 min for (3), and 15 min for (4)) the solvent was elimi-
nated under reduced pressure leaving an off-white solid. Crystal-
lization was effected in a mixture of hexane/dichloromethane at
2.1.2. Route B
In a 100 mL round bottom flask with 70 mL of dry toluene were
added [ReBr(CO)5] (0.25 g, 0.62 mmol) and an equimolar amount of
the corresponding phosphine (PPh3, 0.162 g; PMePh2, 0.124 g;
PMe2Ph, 0.086 g and PMe3, 0.047 g); the reaction mixture was
stirred and set to reflux temperature. The reaction was monitored
by 31P NMR. Once the complex was detected as the only product
(40 min, complex (b); 30 min, complex (c); 25 min, complex (d);
10 min, complex (e)) the reaction was allowed to stand at room
temperature (25 ꢀC) for around 10 min. K[N(SPPh2)2] (0.30 g,
0.62 mmol) were added to the reaction mixture and set to toluene
reflux temperature for 1 h, PPh3; 168 h, PMePh2; 96 h, PMe2Ph;
21 h, PMe3. The solvent was evaporated to dryness under reduced
pressure leaving a whitish powder. The solvent was reduced under
vacuum and crystallization from a mixture of hexane/dichloro-
methane afforded complex (1) in 87% yield (0.53 g, 0.54 mmol),
compound (2) in 58% (0.33 g, 0.36 mmol), complex (3) in 67%
(0.35 g, 0.41 mmol) and compound (4) in 74% (0.36 g, 0.46 mmol).
4
ꢀC for several days yielding crystalline powders in all cases.
2.1.1.1. [Re(CO)3(PPh3){Ph2P(S)NP(S)Ph2-k2S}] (1). 0.587 g, 97%
yield; 192e194 ꢀC nmax(KBr)/cmꢁ1 2019s, 1921s, 1896s (CO); 1209s
nas(P2N); 571m nas(PS); 524m ns(PS). nmax(CH2Cl2)/cmꢁ1 2023 vs,
1933 vs, 1899 vs (CO). 1H NMR (CDCl3, 300 MHz):
d
/ppm: 8.1e8.02
[m, Ho(PNP)], 7.7e7.1 [m, aromatic protons: PNP and PPh3]. 13C{1H}
NMR (CDCl3, 75.6 MHz):
d/ppm: 138.85e136.71 [m, Ci (PNP)];
134.48 [d, Co (PPh3), 2JCo-P ¼ 10 Hz], 131.44e131.29 [m, Co (PNP)],
130.94e130.78 [m, Ci (PPh3)], 130.29 [s, Cp (PNP)], 130.04 [s, Cp
(PPh3)], 127.27e127.55 [m, Cm (PNP) and Cm (PPh3)], 190.1 [s, broad,
CO], 189.9 [s, broad, CO], 189 [s, broad, CO]. 31P{1H} NMR (CDCl3,
121.7 MHz):
d
/ppm: 40.4 [d, (PNP) 3JPNP-PPh3 ¼ 18 Hz], 8.1 [t, (PPh3)
3JPPh3-PNP ¼ 18 Hz]. MS (m/e): 982 [M]þ, 925 [M-2CO]þ.
2.1.3. Route C
Complexes (1), (2), (3), and (4) were prepared by Route C as
follows: [ReBr(CO)5] (0.25 g, 0.62 mmol) and K[N(SPPh2)2] (0.30 g,
0.62 mmol) were added to a 70 mL solution of the corresponding
phosphine in an equimolar amount (PPh3, 0.161 g; PMePh2,
0.123 g; PMe2Ph, 0.085 g and PMe3, 0.047 g) of dry toluene in
a 100 mL round bottom flask and set to reflux temperature.
Reaction times were determined by 31P{1H} NMR monitoring (2 h
for complex (1), 165 h for (2), 93 h for (3), and 19 h for (4)). After
the reaction was completed the KBr was filtered off. Evaporation
under vacuum afforded solid materials. The yields were as follows:
86% for (1) (0.53 g, 0.54 mmol); 60% for (2) (0.33 g, 0.37 mmol);
67% for (3) (0.35 g, 0.41 mmol); and 74% for (4) (0.36 g,
0.46 mmol). (Tables 1,2)
2.1.1.2. [Re(CO)3(PMePh2){Ph2P(S)NP(S)Ph2-k2S}] (2). 0.5437 g, 94%
yield; 205e207 ꢀC nmax(KBr)/cmꢁ1 2018s, 1925s, 1898s (CO); 1237s
nas(P2N); 569m nas(PS); 512m ns(PS). nmax(CH2Cl2)/cmꢁ1 2024 vs,
1933 vs, 1900 vs (CO). 1H NMR (CDCl3, 300 MHz):
d/ppm: 8.1e8.04
[m, Ho(PNP)], 7.7e7.1 [m, aromatic protons: PNP and PMePh2], 2.25
2
[d, HMe, PMePh2, JPH ¼ 8 Hz]. 13C{1H} NMR (CDCl3, 75.6 MHz):
d/
ppm: 139.2e136.7 [m, Ci (PNP)]; 132.6 [d, Co (PMePh2), 2JCo-P
¼ 10 Hz], 131.49e131.33 [m, Co (PNP)], 130.75e130.6 [m, Ci
(PMePh2)], 130.4 [s, Cp (PNP)], 130 [s, Cp (PMePh2)], 128.4e127.7 [m,
Cm (PNP) and Cm (PMePh2)], 13.87 [d, CMe, PMePh2, JC-P ¼ 30 Hz],
190.2 [s, broad, CO],190.1 [s, broad, CO], 189.3 [s, broad, CO]. 31P{1H}
3
NMR (CDCl3, 121.7 MHz):
d
/ppm: 40.3 [d, (PNP) JPNP-PMePh2
¼
3
19.8 Hz], ꢁ9.8 [t, (PMePh2) JPMePh2-PNP ¼ 19.8 Hz]. MS (m/e): 920
[M]þ, 863 [M-2CO]þ, 835 [M-3CO]þ.
Table 1
2.1.1.3. [Re(CO)3(PMe2Ph){Ph2P(S)NP(S)Ph2-k2S}] (3). 0.519 g, 95%
yield; 216e218 ꢀC nmax(KBr)/cmꢁ1 2013 vs, 1916 vs, 1888 vs (CO);
1211s nas(P2N); 571m nas(PS); 512m ns(PS). nmax(CH2Cl2)/cmꢁ1 2021
Crystal data for (1) and (2).
(1)
(2)
Molecular formula
M
C45H35ReNO3P3S2
980.97
291(2)ꢀK
C40H33ReNO3P3S2
918.90
100(2)ꢀK
vs, 1930 vs, 1897 vs (CO). 1H NMR (CDCl3, 300 MHz):
d/ppm:
Temperature
Crystal size (mm)
Crystal system
Space group
a (Å)
8.1e8.03 [m, Ho(PNP)], 7.6e7.2 [m, aromatic protons: PNP and
0.27 ꢂ 0.07 ꢂ 0.04
0.50 ꢂ 0.38 ꢂ 0.36
Monoclinic
P21/c
22.5771(15)
17.1922(11)
20.5151(13)
2
PMe2Ph], 1.97 [d, HMe, PMe2Ph, JPH ¼ 8 Hz]. 13C{1H} NMR (CDCl3,
Triclinic
75.6 MHz): d/ppm: 139.5e136.2 [m, Ci (PNP)]; 131.50e131.34 [m, Co
P-1
9.7428(6)
9.8471(6)
21.2468(13)
93.876(1)
93.168(1)
91.843(1)
2029.3(2)
2
(PNP)], 131.04 [s, Cp (PNP)], 130.66e130.5 [m, Ci (PMe2Ph)],129.9 [d,
Co (PMe2Ph), 2JCo-P ¼ 10 Hz],130.6 [s, Cp (PMe2Ph)],128.5e127.8 [m,
Cm (PNP) and Cm (PMe2Ph)], 13.82 [d, CMe, PMePh2, JC-P ¼ 30 Hz],
b (Å)
c (Å)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
190.3 [s, broad, CO], 190.17 [s, broad, CO], 189.7 [s, broad, CO]. 31P
110.172(1)
3
{1H} NMR (CDCl3, 121.7 MHz):
d
/ppm: 40.2 [d, (PNP) JPNP-
¼ 21.2 Hz], ꢁ25.9 [t, (PPh3) 3JPMe2Ph-PNP ¼ 21.2 Hz]. MS (m/e):
V (Å3)
Z
7474.7(8)
8
1.53e25.00
37678
13158 (Rint ¼ 0.0302)
R1 ¼ 0.0268,
wR2 ¼ 0.0647
R1 ¼ 0.0295,
wR2 ¼ 0.0659
PMe2Ph
858 [M]þ, 801 [M-2CO]þ, 773 [M-3CO]þ, 635 [M-3CO, PMe2Ph]þ.
q
Range for data collection (ꢀ)
1.92e25.36
17196
Reflections collected
2.1.1.4. [Re(CO)3(PMe3){Ph2P(S)NP(S)Ph2-k2S}] (4). 0.479 g, 98%
yield; 233e235 ꢀC nmax(KBr)/cmꢁ1 2019 vs, 1925 vs, 1887 vs (CO);
1223s nas(P2N); 572m nas(PS); 512m ns(PS). nmax(CH2Cl2)/cmꢁ1 2020
Independent reflections
7439 (Rint ¼ 0.0432)
R1 ¼ 0.0440,
wR2 ¼ 0.0891
R1 ¼ 0.0555,
wR2 ¼ 0.0937
Final R indices [F2> 2 (F2)]
s
vs, 1928 vs, 1894 vs (CO). 1H NMR (CDCl3, 300 MHz):
d
/ppm:
R indices (all data)
8.13e8.05 [m, Ho(PNP)], 7.7e7.2 [m, aromatic protons: PNP and