1490
J.W. Faller et al. / Journal of Organometallic Chemistry 693 (2008) 1478–1493
3
4
3
P, syn, dd, JHH = 6.1 Hz, JPH = 6.0 Hz); 4.34 (1H, allyl-H,
ddd, allyl-H, trans to P, syn, JHH = 2.5 Hz, JHH =
3
cis to P, syn, d, JHH = 6.1 Hz); 4.03 (1H, m, CH2); 3.92
7.5 Hz, JPH = 7.2 Hz); 3.71 (1H, ddd, allyl-H, cis to P, syn,
3
(1H, m, CH2); 3.66 (1H, allyl-H, trans to P, anti, dd,
3JHH = 12.6 Hz, JPH = 10.8 Hz); 3.09 (1H, allyl-H, cis to
4JHH = 2.2 Hz, JHH = 6.9 Hz, JPH = 2.2 Hz); 3.12 (1H,
3
dd, allyl-H, trans to P, anti, JHH = 14.2 Hz, JPH = 10.6
Hz); 3.17 (1H, d, allyl-H, cis to P, anti, JHH = 12.8 Hz).
3
1
3
P, anti, d, JHH = 12.6 Hz). At ꢀ20 ꢁC the H resonances
at d 4.34 and d 3.09 broaden owing to exchange between
them and the dppm methylene resonances at d 4.03 and d
3.92 also broaden and coalesce. Some averaging of lines
within the multiplet at d 5.66 is also observed at that tem-
perature. Slight broadening of the resonances at d 5.04 and
d 3.66 only starts to occur upon raising the temperature to
0 ꢁC. 31P NMR (162 MHz, CD2Cl2, 22 ꢁC) d: 62.3 (P@S, d,
JPP = 59.6 Hz); 30.1 (P(III), d, JPP = 59.6 Hz). 13C NMR
(101 MHz, CD2Cl2, 20 ꢁC) d: 134.0 (2C, Ph-C); 133.1
(4C, d, Ph-C, JPC = 14.8 Hz); 133.3 (2C, Ph-C); 132.1
(4C, d, Ph-C, JPC = 10.6 Hz); 129.8 (10C, m, Ph-C);
126.5 (2C, d, Ph-CP, JPC = 84.1 Hz); 120.1 (1C, d, allyl-
CH, JPC = 5.9 Hz); 76.2 (1C, br, allyl-CH2, trans to P,
JPC ꢁ30 Hz); 65.6 (1C, br, allyl-CH2, cis to P); 37.9 (1C,
31P NMR (162 MHz, CD2Cl2) d: 42.2 (P@S); 19.3 (P(III)).
31P NMR (162 MHz, CD2Cl2) d: 46.7 (P@S); 18.1 (P(III)).
Anal. Calc. for C37H33F6Fe1P2- Pd1S1Sb1: C, 45.83; H,
3.43. Found: C, 45.70; H, 3.42%. At ꢀ100ꢁC, the complex
exists as two diastereomers in a 1.0:0.6 ratio that involve
exchange by a twist of the ligand backbone which has a bar-
rier of 10.6 kcal molꢀ1 31P NMR (162 MHz, CD2Cl2,
.
ꢀ100ꢁC) Major diastereomer d: 46.9 (P@S); 16.7 (P(III)).
Minor diastereomer d: 46.8 (P@S); 18.0 (P(III)).
4.3.5. [Pd(g3-C3H5)(xantphos(S))][SbF6] (2e)
1H NMR (400 MHz, CD2Cl2) d: 7.85 (1H, ddd, xan-
4
3
5
thene-H, JHH = 1.4 Hz, JHH = 7.9 Hz, JPH = 1.0 Hz);
4
3
7.72 (1H, dd, xanthene-H, JHH = 1.4 Hz, JHH = 7.9 Hz);
7.66–7.18, 7.07 (22H, m, Ph-H, xanthene-H); 6.76 (1H,
1
1
dd, PCH2, JPC = 19.9 Hz, JPC = 56.7 Hz).
4
3
3
ddd, xanthene-H, JHH = 1.4 Hz, JHH = 7.9 Hz, JPH
=
4
10.2 Hz); 6.65 (1H, ddd, xanthene-H, JHH = 1.4 Hz,
4.3.3. [Pd(g3-C3H5)(diphos(S))][SbF6] (2b)
3JHH = 7.9 Hz, JPH = 15.2 Hz); 5.29 (1H, dddd, allyl-H,
3
1H NMR (500 MHz, CD2Cl2) d: 7.90–7.44 (20H, m, Ph-
3
central, JHH = 6.9 Hz, 7.5 Hz, 12.8 Hz, 13.6 Hz); 4.72
3
H); 5.66 (1H, dddd, allyl-H, central, JHH = 7.0, 7.6, 12.6,
4
3
(1H, allyl-H, trans to P, syn, ddd, JHH = 2.2 Hz, JHH
=
14.0 Hz); 4.92 (1H, allyl-H, trans to P, syn, ddd,
7.5 Hz, JPH = 7.3 Hz); 3.72 (1H, allyl-H, cis to P, syn, dd,
4JHH = 2.0 Hz, JHH = 7.6 Hz, JPH = 6.2 Hz); 3.74 (1H,
3
4JHH = 2.2 Hz, JHH = 6.8 Hz); 3.25 (1H, allyl-H, trans to
3
3
allyl-H, trans to P, anti, dd, JHH = 14.0 Hz, JPH
14.0 Hz); 3.69 (1H, allyl-H, cis to P, syn, dd, JHH
=
=
3
P, anti, dd, JHH = 13.6 Hz, JPH = 10.6 Hz); 2.30 (1H,
allyl-H, cis to P, anti, d, JHH = 12.8 Hz); 1.79 (3H, s,
4
3
3
2.0 Hz, JHH = 7.0 Hz); 2.93 (1H, allyl-H, cis to P, anti,
CH3); 1.67 (3H, s, CH3). 31P NMR (162 MHz, CD2Cl2)
d: 42.2 (P@S); 19.3 (P(III)). 13C NMR (126 MHz, CD2Cl2)
d: 155.0 (1C, m, OC); 153.2 (1C, m, OC); 134.6–128.9,
125.8, 125.1, 119.3, 119.0, 116.2, 115.5 (34C, aromatic-C);
119.4 (1C, d, allyl-CH, JPC = 6.0 Hz); 80.1 (1C, d, allyl-
CH2, trans to P, JPC = 32.3 Hz); 66.2 (1C, d, allyl-CH2,
cis to P, JPC = 2.2 Hz) 35.4, 30.8, 28.2 (3C, C(CH3)2,
CH3). Anal. Calc. for C42H37F6OP2PdSSb: C, 50.75; H,
3.75. Found: C, 50.65; H, 3.70%.
d, JHH = 12.6 Hz); 3.18–2.80 (4H, m, CH2). 31P NMR
3
(162 MHz, CD2Cl2) d: 44.1 (P@S, d, JPP = 19.8 Hz); 13.9
(P(III), d, JPP = 19.8 Hz). 13C NMR (126 MHz, CD2Cl2)
d: 134.1 (1C, d, Ph-C, JPC = 3.0 Hz); 133.9 (1C, d, Ph-C,
JPC = 3.0 Hz); 133.2 (2C, d, Ph-C, JPC = 13.0 Hz); 132.7
(2C, d, Ph-C, JPC = 12.6 Hz); 132.2 (1C, d, Ph-C,
JPC = 2.5 Hz); 132.0 (1C, d, Ph-C, JPC = 2.5 Hz); 131.7
(2C, d, Ph-C, JPC = 10.4 Hz); 131.6 (2C, d, Ph-C, JPC
=
10.4 Hz); 131.2 (1C, d, Ph-CP, JPC = 44.3 Hz); 130.6 (1C,
d, Ph-CP, JPC = 44.8 Hz); 130.1 (2C, d, Ph-C,
JPC = 12.2 Hz); 130.0 (2C, d, Ph-C, JPC = 12.2 Hz); 129.9
(2C, d, Ph-C, JPC = 10.2 Hz); 129.8 (2C, d, Ph-C, JPC
10.2 Hz); 128.0 (1C, d, Ph-CP, JCP = 82.5 Hz); 127.8 (1C,
d, Ph-CP, JPC = 84.1 Hz); 120.3 (1C, d, allyl-CH, JPC
6.0 Hz); 80.3 (1C, dd, allyl-CH2, trans to P, JPC = 28.3
Hz, 1.6 Hz); 66.2 (1C, d, allyl-CH2, cis to P, JPC = 3.2
Hz); 26.2 (1C, d, PCH2, JPC = 52.9 Hz); 22.1 (1C, dd,
4.3.6. Preparation of Pd(HC(PPh2)(P(S)Ph2)2)Cl2 (3)
The bis-sulfide of 1,1,1-tris-diphenylphospinomethane Æ
LiCl (0.26 mmol, 17.6 mg) was combined with Pd-
(C6H5CN)2Cl2 in dry CH2Cl2 and stirred at R.T. for
30 min, then filtered through Celite. The solvent was
removed by rotary evaporation and the resulting orange
solid was washed with ether and the desired product was
collected in 78% yield. 31P NMR (162 MHz, CD2Cl2,
=
=
1
1
2
PCH2, JPC = 26.5, JPC = 5.1 Hz). Anal. Calc. for
C29H29F6P2PdSSb: C, 42.81; H, 3.59. Found: C, 42.99;
H, 3.62%.
2
ꢀ80 ꢁC) d: 64.1 (P@S, d, JPP = 47 Hz); 52.1 (P(III), dd,
2JPP = 47, 5 Hz); 33.6 (P@S, d, JPP = 5 Hz). Anal. Calc.
2
for C37H31Cl2P3Pd1S2 Æ 0.25 CH2Cl2: C, 53.82; H, 3.82.
Found: C, 53.48; H, 3.80%.
4.3.4. [Pd(g3-C3H5)(dppf(S))][SbF6] (2d)
1H NMR (500 MHz, CD2Cl2) d: 7.75–7.67 (6H, m, Ph-
H); 7.60–7.43 (12H, m, Ph-H); 7.40–7.35 (2H, m, Ph-H);
4.3.7. Preparation of [Pd(g3-C3H5)(HC(PPh2)-
(P(S)Ph2)2)][SbF6] (4)
[Pd(g3-C3H5)Cl]2 (125 mg, 0.34 mmol) was dissolved in
CH2Cl2 (10 mL) in a Schlenk flask. To the yellow solution
3
5.58 (1H, dddd, allyl-H, central, JHH = 6.9 Hz, 7.5 Hz,
12.8 Hz, 14.2 Hz); 4.76 (1H, m, Cp-H); 4.71 (3H, m, Cp-
H); 4.54 (3H, m, Cp-H); 4.45 (1H, m, Cp-H); 4.12 (1H,