264
M.S. Balakrishna et al. / Inorganica Chimica Acta 372 (2011) 259–265
NMR (400 MHz, CDCl3): 4.45 (d, JHH = 14.8 Hz OCH2, 2H), 4.02 (t,
7 Hz, OCH2, 2H), 2.82 (s, SCH2, 2H), 2.71 (s, SCH2, 2H), 2.37 (s,
SCH3, 3H), 2.16 (s, SCH3, 3H), 1.53 (s, tBu, 18H). 31P{1H} NMR
(161.8 MHz, CDCl3): 104.6 (s), 76.9 (s, Pd–P).
6.2.6. Synthesis of cis-[RuCl(
(7)
g
6-p-cymene){tBuNP(OCH2CH2SCH3)}2]Cl
6-p-cymene)Cl2]2
A dichloromethane (5 mL) solution of [Ru(
g
(0.050 g, 0.81 mmol) was added dropwise to cis-{tBuN-
P(OCH2CH2SCH3)}2 (0.063 g, 0.163 mmol) in dichloromethane
(5 mL) at room temperature. The reaction mixture was stirred for
6 h. The clear red colored solution obtained was concentrated to
4 mL; layered with 2 mL of petroleum ether and kept at room tem-
perature for two days to afford 7 as red crystalline compound.
Yield: 91% (0.102 g). Mp: 172–174 °C (dec). Anal. Calc. for
6.2.2. Synthesis of cis-[{PdCl2}2{tBuNP(OCH2CH2SCH3)}2] (3)
To
a
solution of cis-{tBuNP(OCH2CH2SCH3)}2 (0.035 g,
0.091 mmol) in dichloromethane (10 mL) was added dropwise
[Pd(COD)Cl2] (0.052 g, 0.181 mmol) in the same solvent (5 mL)
and the reaction mixture was stirred well at room temperature
for 8 h. The yellow precipitate formed was filtered and dried under
vacuum to give analytically pure product of 3. Yield: 78% (0.053 g).
Mp: 192–194 °C (dec). Anal. Calc. for C14H32N2P2O2S2Pd2Cl4: C,
22.68; H, 4.35; N, 3.78; S, 8.65. Found: C, 22.60; H, 4.48; N, 3.83;
S, 8.75%. 1H NMR (400 MHz, DMSO-d6): 4.52 (s, OCH2, 4H), 2.86
C
24H46N2P2O2S2RuCl2: C, 41.61; H, 6.69; N, 4.04; S, 9.25. Found:
C, 41.55; H, 6.75; N, 4.15; S, 9.29%. 1H NMR (400 MHz, CDCl3):
5.15 (d, JHH = 6.4 Hz, Cymene phenyl, 2H), 4.95 (d, JHH = 6.4, Hz,
Cymene phenyl, 2H), 4.73 (t, JHH = 6.4 Hz, OCH2, 2H), 4.69 (t,
JHH = 6.4 Hz, OCH2, 2H), 3.02 (t, JHH = 6 Hz, SCH2, 2H), 2.76 (septet,
CH, 1H), 2.58 (t, JHH = 6 Hz, SCH2, 2H), 2.25 (s, SCH3, 3H), 2.19 (s,
t
t
(s, SCH2, 4H), 2.79 (S, SCH3, 4H), 1.59 (s, Bu, 18H). 31P{1H} NMR
SCH3, 3H), 2.01 (s, CH3, 3H), 1.61 (s, Bu, 18H), 1.33 (d, JHH = 7.2 Hz,
(161.8 MHz, DMSO-d6): 104.6 (s).
CH3, 6H). 31P{1H} NMR (161.8 MHz, CDCl3): 116.8 (d), 108.5(d),
2JPP = 60 Hz. MS (EI): m/z 657.3 (M–Cl).
6.2.3. Synthesis of trans-[PdCl2{(tBuNP(OCH2CH2SCH3))2}2] (4)
To a stirred solution of cis-{tBuNP(OCH2CH2SCH3)}2 (0.048 g,
0.124 mmol) in dichloromethane (5 mL) was added dropwise a
solution of [Pd(SMe2)2Cl2] (0.019 g, 0.062 mmol) also in of dichlo-
romethane (5 mL) and the clear yellow solution was stirred at
room temperature for 4 h. The solution was concentrated and lay-
ered with petroleum ether and stored ꢁ25 °C for two days to afford
4 as yellow crystalline compound. Yield: 68% (0.040 g). Mp: 140–
144 °C (dec). Anal. Calc. for C28H64N4P4O4S4PdCl2: C, 35.38; H,
6.79; N, 5.89; S, 13.49. Found: C, 35.37; H, 6.75; N, 5.81; S,
13.34%. 1H NMR (400 MHz, CDCl3): 4.22 (t, JHH = 3.6 Hz, OCH2,
4H), 3.98 (t, JHH = 6.8 Hz, OCH2, 4H), 2.72 (s, SCH2, 8H), 2.08 (s,
SCH3, 6H), 2.07 (s, SCH3, 6H), 1.43 (s, tBu, 36H). 31P{1H} NMR
(161.8 MHz, CDCl3): 129.6 (s), 83.2(s, Pd–P).
6.2.7. Synthesis of cis-[RhCl(COD){tBuNP(OCH2CH2SCH3)}2] (8)
A dichloromethane (5 mL) solution of [Rh(COD)Cl]2 (0.044 g,
0.089 mmol) was added dropwise to a well-stirred solution of
cis-{tBuNP(OCH2CH2SCH3)}2 (0.069 g, 0.178 mmol) in the same sol-
vent (5 mL) at room temperature and the stirring was continued
for 6 h. The yellow colored solution was concentrated to 4 mL
and layered with 2 mL of petroleum ether and stored at ꢁ25 °C
to afford 8 as yellow crystalline compound. Yield: 65% (0.073 g).
Mp: 146–148 °C (dec). Anal. Calc. for C22H44N2P2O2S2RhCl: C,
41.74; H, 7.01; N, 4.42; S, 10.13. Found: C, 41.77; H, 7.11; N,
4.56; S, 10.07%. 1H NMR (400 MHz, CDCl3): 5.40 (d, JHH = 3.8 Hz,
CH, 4H), 4.45 (m, OCH2, 4H), 2.44 (d, JHH = 4.2 Hz, CH2, 8H), 2.82
t
(m, SCH2, 4H), 2.07 (s, SCH3, 3H), 2.06 (s, SCH3, 3H), 1.55 (s, Bu,
18H). 31P{1H} NMR (161.8 MHz, CDCl3): 133.6 (s), 102.9 (d,
JRhP = 221 Hz, Rh-P).
6.2.4. Synthesis of cis-[PdCl2(PEt3){tBuNP(OCH2CH2SCH3)}2] (5)
A dichloromethane solution (5 mL) of [Pd(PEt3)Cl2]2 (0.028 g,
0.048 mmol) was added dropwise to cis-{tBuNP(OCH2CH2SCH3)}2
(0.037 g, 0.096 mmol) in dichloromethane (5 mL) at room temper-
ature. The reaction mixture was stirred for 8 h and then concen-
trated to 5 mL. The solution was layered with 2 mL of diethyl
ether and placed at ꢁ25 °C for 18 h to afford 5 as yellow crystalline
solid. Yield: 65% (0.043 g). Mp: 166–168 °C (dec). Anal. Calc. for
6.2.8. Synthesis of cis-[PtCl2{tBuNP(OCH2CH2SCH3)}2] (9)
This was synthesized by a procedure similar to that of 2, using
cis-{tBuNP(OCH2CH2SCH3)}2
(0.022 g,
0.057 mmol)
and
[Pt(COD)Cl2] (0.021 g, 0.057 mmol). Yield: 76% (0.028 g). Mp:
210–212 °C (dec). Anal. Calc. for C14H32N2P2O2S2PtCl2: C, 25.77;
H, 4.94; N, 4.29; S, 9.82. Found: C, 25.86; H, 4.96; N, 4.25; S,
9.77%. 1H NMR (400 MHz, CDCl3): 4.55 (d, JHH = 14.8 Hz OCH2,
2H), 4.15 (t, JHH = 8.2 Hz, OCH2, 2H), 2.85 (s, SCH2, 2H), 2.78 (s,
t
C
20H47N2P3O2S2PdCl2: C, 35.22; H, 6.95; N, 4.11; S, 9.40. Found:
SCH2, 2H), 2.38 (s, SCH3, 3H), 2.12 (s, SCH3, 3H), 1.45 (s, Bu, 18H).
C, 35.35; H, 6.83; N, 4.20; S, 9.47%. 1H NMR (400 MHz, CDCl3):
4.23 (t, JHH = 7.6 Hz, OCH2, 2H), 4.06 (t, JHH = 7.2 Hz, OCH2, 2H),
2.74 (m, SCH2, 4H), 2.16 (s, SCH3, 3H), 2.14 (s, SCH3, 3H), 2.09 (q,
31P{1H} NMR (161.8 MHz, CDCl3): 106.2 (s), 49.30 (s, Pt–P),
1JPtP = 4750 Hz.
t
JHH = 10.8 Hz, P-CH2, 6H) 1.43 (s, Bu, 18H), 0.94 (t, JHH = 7.6 Hz, P-
6.2.9. Synthesis of cis-[(AuCl)2{tBuNP(OCH2CH2SCH3)}2] (10)
CH3, 9H). 31P{1H} NMR (161.8 MHz, CDCl3): 131.2 (d), 84.3 (dd),
To
a
solution of cis-{tBuNP(OCH2CH2SCH3)}2 (0.053 g,
2
2
24.0 (d, JPNP = 3.8 Hz, JPPdP = 12.3 Hz).
0.138 mmol) in 4 mL of dichloromethane added a solution of
[Au(SMe2)Cl] (0.020 g, 0.069 mmol) in dichloromethane (8 mL) at
room temperature. The reaction mixture was stirred under dark
for 4 h. The clear solution was concentrated and layered with
petroleum ether to get 10 as colorless compound. Yield: 86%
(0.051 g). Mp: 230–232 °C (dec). Anal. Calc. for C14H32N2P2O2-
S2Au2Cl2: C, 19.75; H, 3.79; N, 3.29; S, 7.53. Found: C, 19.82; H,
3.76; N, 3.68; S, 7.41%. 1H NMR (400 MHz, CDCl3): 4.12 (br s,
6.2.5. Synthesis of cis-[{PdCl(
A solution of [PdCl(
3-C3H5)]2 (0.024 g, 0.066 mmol) in dichlo-
g
3-C3H5){tBuNP(OCH2CH2SCH3)}2] (6)
g
romethane (5 mL) was added dropwise to a solution of cis-{tBuN-
P(OCH2CH2SCH3)}2 (0.025 g, 0.066 mmol) in the same solvent
(8 mL) at room temperature and the reaction mixture was stirred
for 4 h. The pale yellow colored solution was concentrated and lay-
ered with petroleum ether to obtain 6 as yellow crystalline solid.
Yield: 82% (0.041 g). Mp: 120–122 °C (dec). Anal. Calc. for
t
OCH2, 4H), 2.79 (br s, SCH2, 4H), 2.12 (S, SCH3, 6H), 1.54 (s, Bu,
18H). 31P{1H} NMR (161.8 MHz, CDCl3): 100.3 (s).
C
20H42N2P2O2S2Pd2Cl2: C, 31.92; H, 5.62; N, 3.72; S, 8.52. Found:
6.2.10. Typical procedure for Suzuki–Miyaura cross-coupling reactions
In a two-necked round-bottom flask under an atmosphere of
nitrogen was placed the appropriate amount of catalyst solution,
and 5 mL of methanol was added to it. The correct amount of cat-
alyst was added as a methanol solution made up by multiple vol-
C, 31.97; H, 5.61; N, 3.78; S, 8.47%. 1H NMR (400 MHz, CDCl3):
5.68 (br s, CH2, 6H), 4.71 (br s, CH, 4H), 4.28 (m, OCH2, 4H), 2.82
(br s SCH2, 4H), 2.13 (s, SCH3, 6H), 1.53 (s, Bu, 18H). 31P{1H} NMR
t
(161.8 MHz, CDCl3): 121.1 (s).