Article
Organometallics, Vol. 29, No. 6, 2010 1449
(CD2Cl2): δ 107.9 (s). Anal. Calcd for C30H45Cl2N2O3PPd: C,
52.22; H, 6.57; N, 4.06. Found: C, 52.11; H, 6.56; N, 3.98.
[PdCl2(IPr){P(OEt)3}] (6b). A Schlenk tube was charged with
[Pd(μ-Cl)Cl(IPr)]2 (0.294 g, 0.26 mmol) suspended in dichloro-
methane (10 mL), and an excess of P(OEt)3 (0.1 mL, 0.58 mmol)
was added. The solution was stirred at room temperature for
30 min. Methanol (5 mL) was added, and the reaction mixture
was concentrated to 2 mL. The supernatant solution was
removed and MeOH (2 mL) was added to the precipitate. The
solution was concentrated to 1 mL, the supernatant solu-
tion removed with a syringe and the solid was dried in vacuo.
The complex was obtained as a yellow solid (0.259 g, 68%).
Single crystals suitable for X-ray diffraction were obtained by
slow diffusion of methanol in a dichloromethane solution of the
[PdCl2(IPr){P(OC6H3-2,4-tBu2)3}] (6e). A Schlenk tube was
charged with tris(2,4-di-tert-butylphenyl)phosphite (0.231 g,
0.36 mmol), [Pd(μ-Cl)Cl(IPr)]2 (0.201 g, 0.18 mmol), and di-
chloromethane (10 mL) was added. The reaction mixture was
stirred at room temperature for 30 min, concentrated in vacuo to
5 mL, and methanol (10 mL) was added. The solution was
concentrated to 7 mL, the supernatant was removed with a
syringe, and the precipitate was washed with methanol (3 ꢀ
10 mL). The product was obtained as a pale-yellow powder
(0.371 g, 86%). Single crystals suitable for X-ray diffraction
were obtained by slow diffusion of methanol in a dichloro-
methane solution of the complex. 1H NMR (CD2Cl2): δ 1.01 (d,
3
3
12H, JHH = 6.9 Hz, CHCH3), 1.13 (d, 12H, JHH = 6.6 Hz,
CHCH3), 1.29 (br s, 27H, C(CH3)3), 1.37 (br s, 27H, C(CH3)3),
3.03 (pseudo sept, 4H, 3JHH = 6.8 Hz, CHCH3), 6.77 (dd, 3H,
J = 8.6 Hz, J = 2.6 Hz, CH phosphite), 7.08 (d, 2H, J = 2.3 Hz,
CH carbene), 7.21 (br d, 4H, CH carbene), 7.28 (m, 3H, CH
phosphite), 7.36-7.48 (m, 5H, CH). 13C{1H} NMR (CD2Cl2): δ
1
3
complex. H NMR (CD2Cl2): δ 1.08 (t, 9H, JHH = 7.0 Hz,
OCH2CH3), 1.08 (d, 12H, JHH = 6.9 Hz, CHCH3), 1.37 (d,
3
12H, 3JHH = 6.65 Hz, CHCH3), 3.10 (pseudo sept, 4H, 3JHH
=
6.8 Hz, CHCH3), 3.85 (m, 6H, OCH2CH3), 7.14 (d, 2H, J = 2.2
Hz, CH), 7.33 (br d, 4H, CH), 7.49 (br dd, 2H, CH). 13C{1H}
NMR (CD2Cl2): δ 16.25 (d, 3JCP = 7.0 Hz, O-CH2-CH3), 23.0
(s, iPr), 26.4 (s, iPr), 29.0 (s, iPr), 62.3 (s, O-CH2-CH3), 124.0 (s,
i
i
i
22.7 (s, Pr), 26.4 (s, Pr), 28.8 (s, Pr), 30.5 (C(CH3)3), 31.6
(C(CH3)3), 34.6 (C(CH3)3), 35.3 (C(CH3)3), 118.8 (d, JCP = 9.8
Hz, CH phosphite), 123.6 (s, CH), 124.0 (s, CH), 125.0 (s, CH),
125.1 (d, 4JCP = 8.9 Hz, C4H-C5H), 130.1 (s, CH), 135.4 (s, C
NHC), 138.6 (d, JCP = 5.9 Hz, C phosphite), 145.9 (s, C
phosphite), 147.0 (s, C NHC), 148.2 (d, JCP = 5.8 Hz, C
4
CH aromatic), 124.8 (d, JCP = 8.2 Hz, C4H-C5H), 130.2
(s, CH aromatic), 135.7 (s, C aromatic), 147.2 (s, C aromatic),
171.9 (d, 2JCP = 290.9 Hz, C carbene). 31P{1H} NMR (CD2Cl2):
δ 103.3 (s). Anal. Calcd for C33H51Cl2N2O3PPd: C, 54.14; H,
7.02; N, 3.83. Found: C, 54.02; H, 7.08; N, 3.74.
2
phosphite), 168.1 (d, JCP = 306.3 Hz, C carbene). 31P{1H}
NMR (CD2Cl2): δ 93.1 (s). Anal. Calcd for C70H101Cl4-
N2O3PPd: C, 64.78; H, 7.84; N, 2.16. Found C, 64.77; H, 7.78;
N, 2.06.
[PdCl2(IPr){P(OiPr)3}] (6c). A Schlenk tube was charged
with [Pd(μ-Cl)Cl(IPr)]2 (0.221 g, 0.19 mmol) suspended in
dichloromethane (10 mL), and P(OiPr)3 (0.1 mL, 0.40 mmol)
was added. The solution was stirred at room temperature for
30 min and concentrated to 5 mL, and cyclohexane (5 mL) was
added. The solution was further concentrated to 1 mL, the
supernatant solution removed with a syringe, and the precipitate
was washed with cyclohexane (2 ꢀ 2 mL) and dried in vacuo.
The complex was obtained as a shiny yellow solid (0.227 g,
75%). Single crystals suitable for X-ray diffraction were ob-
tained by slow evaporation of a dichloromethane solution of the
complex. 1H NMR (CD2Cl2): δ 1.07 (overlapping d, 30H,
[PdCl2(IPr){P(OCH2CF3)3}] (6f).
A Schlenk tube was
charged with [Pd(μ-Cl)Cl(IPr)]2 (0.226 g, 0.20 mmol) suspended
in dry THF (2.5 mL), and P(OCH2CF3)3 (0.131 g, 88.2 μL, 0.40
mmol) was added. The solution was stirred at room temperature
for 30 min. The solvent was then evaporated. The product was
obtained analytically pure by recrystallization from THF/
pentane. The complex was obtained as a yellow solid (0.260 g,
3
64%). 1H NMR (CD2Cl2): δ 1.10 (d, 12H, JHH = 6.9 Hz,
CHCH3), 1.38 (d, 12H, 3JHH = 6.7 Hz, CHCH3), 3.01 (pseudo
sept, 4H, JHH = 6.8 Hz, CHCH3), 4.24 (m, 6H, OCH2CF3),
7.21 (d, 2H, J = 2.4 Hz, CH), 7.36 (br d, 4H, CH), 7.52 (br dd,
3
3
3JHH = 6.2 Hz, JHH = 6.9 Hz, OCHCH3 and CCHCH3),
1.37 (d, 12H, 3JHH = 6.7 Hz, CHCH3), 3.11 (pseudo sept, 4H,
3JHH =6.8 Hz, CCHCH3), 4.62 (m, 3H, OCHCH3), 7.12 (d, 2H,
J = 2.2 Hz, CH), 7.33 (br d, 4H, CH), 7.49 (br dd, 2H, CH).
13C{1H} NMR (CD2Cl2): δ 23.0 (s, iPr), 24.05 (d, 3JCP = 4.0 Hz,
2H, CH). 13C{1H} NMR (CD2Cl2): δ 22.9 (s, iPr), 26.5 (s, iPr),
29.1 (s, iPr), 63.6 (q, 2JCF = 37.7 Hz, OCH2), 122.75 (dq, 1JCF
=
278 Hz, 3JCP = 8.7 Hz, CF3), 124.2 (s, CH aromatic), 125.2 (d,
4JCP =8.65 Hz, C4H-C5H), 130.7 (s, CH aromatic), 135.0 (s,
C aromatic), 147.1 (s, C aromatic), 167.2 (d, 2JCP = 302.7 Hz,
C carbene). 31P{1H} NMR (CD2Cl2): δ 108.8 (s). Anal. Calcd
for C33H42Cl2F9N2O3PPd: C, 44.34; H, 4.74; N, 3.13. Found:
C, 44.19; H, 4.82; N, 3.00.
i
i
2
OCHCH3), 26.5 (s, Pr), 29.0 (s, Pr), 71.05 (d, JCP =2.0 Hz,
4
OCHCH3), 124.0 (s, CH aromatic), 124.8 (d, JCP = 7.9 Hz,
C4H-C5H), 130.1 (s, CH aromatic), 135.9 (s, C aromatic), 147.3
(s, C aromatic), 172.6 (d, 2JCP = 291.0 Hz, C carbene). 31P{1H}
NMR (CD2Cl2): δ 97.3(s). Anal. Calcd for C36H57Cl2N2O3PPd:
C, 55.85; H, 7.42; N, 3.62. Found: C, 55.68; H, 7.73; N, 3.41.
[PdCl2(IPr){P(OPh)3}] (6d). A Schlenk tube was charged with
[Pd(μ-Cl)Cl(IPr)]2 (0.302 g, 0.27 mmol) suspended in dichloro-
methane (10 mL), and an excess of P(OPh)3 (0.15 mL, 0.57 mmol)
was added. The solution was stirred at room temperature for
30 min and then concentrated in vacuo (3 mL). Heptane (5 mL)
was added and the solution concentrated to 4 mL. The super-
natant solution was removed with a syringe, and the precipitate
was washed with heptane (3 ꢀ 5 mL). The complex was obtained
as a yellow powder (0.326 g, 70%). Single crystals suitable for
X-ray diffraction were obtained by slow diffusion of heptane in a
dichloromethane solution of the complex. 1H NMR (CD2Cl2): δ
[PdCl2(IPr)(ETPB)] (6g). A Schlenk tube was charged with 4-
ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (ETPB) (0.115 g,
0.71 mmol), [Pd(μ-Cl)Cl(IPr)]2 (0.396 g, 0.35 mmol), and dichloro-
methane (10 mL) was added. The solution was stirred at room
temperature for 30 min, and the solvent was removed in vacuo. The
complex was obtained as a yellow powder in a quantitative yield.
1H NMR (CD2Cl2): δ 0.73 (t, 3H, 3JHH = 7.7 Hz, CH2-CH3),
1.08 (d, 12H, 3JHH = 6.9 Hz, CHCH3), 1.03-1.17 (m, 2H, CH2-
3
CH3), 1.37 (d, 12H, JHH = 6.65 Hz, NCHCH3), 3.02 (pseudo
sept, 4H, 3JHH = 6.8 Hz, CHCH3), 4.11 (d, 6H, 3JHH = 4.5 Hz,
OCH2), 7.11 (d, 2H, J = 2.3 Hz, CH), 7.34 (br d, 4H, CH), 7.51
(br dd, 2H, CH). 13C{1H} NMR (CD2Cl2): δ 7.1 (s, CH2-CH3),
23.3 (s, iPr), 23.5 (s, CH2-CH3), 26.3 (s, iPr), 29.0 (s, iPr), 36.1 (d,
3JCP = 31.2 Hz, C ETPB), 74.5 (d, 2JCP =6.4 Hz, OCH2), 124.2 (s,
CH aromatic), 125.0 (d, 4JCP = 8.6 Hz, C4H-C5H), 130.2 (s, CH
aromatic), 135.4 (s, C aromatic), 146.9 (s, C aromatic), 167.8 (d,
2JCP = 300.5 Hz, C carbene). 31P{1H} NMR (CD2Cl2): δ 87.7 (s).
Anal. Calcd for C33H47Cl2N2O3PPd: C, 54.44; H, 6.51; N, 3.85.
Found: C, 54.59; H, 6.63; N, 3.82.
3
3
1.04 (d, 12H, JHH = 6.9 Hz, CHCH3), 1.21 (d, 12H, JHH
=
6.6 Hz, CHCH3), 3.00 (pseudo sept, 4H, 3JHH =6.8 Hz, CHCH3),
6.95-7.17 (m, 17H, CH), 7.32 (br d, 4H, CH), 7.56 (dd, 2H, CH).
13C{1H} NMR (CD2Cl2): δ 22.9 (s, iPr), 26.5 (s, iPr), 28.9 (s, iPr),
120.6(d, JCP =5.5 Hz, CHPh), 124.3(s, CH), 124.9(s,CH), 125.3
(d, 4JCP = 8.6 Hz, C4H-C5H), 129.9 (s, CH), 130.5 (s, CH), 135.3
(s, C aromatic), 147.1 (s, C aromatic), 151.0 (d, 2JCP = 6.0 Hz,
C-O-P), 167.8 (d, 2JCP = 303.7 Hz, C carbene). 31P{1H} NMR
(CD2Cl2): δ 92.2 (s). Anal. Calcd for C45H51Cl2N2O3PPd: C,
61.68; H, 5.87 ; N, 3.20. Found: C, 62.52; H, 6.55; N, 2.69.
[PdCl2(SIPr){P(OMe)3}] (7a). A Schlenk tube was charged
with [Pd(μ-Cl)Cl(SIPr)]2 (1.313 g, 1.16 mmol) dissolved in
dichloromethane (25 mL), and an excess of P(OMe)3 (0.3 mL,
2.54 mmol) was added. The solution was stirred at room