E. Payet et al. / Journal of Organometallic Chemistry 695 (2010) 1499–1506
1505
2
2
127.8 (s, p-CH(PPh)), 128.1 (d, JP,C 8.0 Hz , m-CH(PPh)), 131.6 (d,
4.54 (2H, d, JC,P 6.0 Hz, PCH2), 5.58 (2H, m, CH(COD)), 6.52 (2H,
d, 3JH,H 7.0 Hz, o-CH(NHPh)), 6.83 (1H, t, 3JH,H 7.0 Hz, p-CH(NHPh)),
2JP,C 18.0 Hz, o-CH(PPh)), 138.9 (d, JP,C 15.0 Hz, Cipso-(PPh)); dP
1
(121.5 MHz, C6D6, 25 °C) –27.6; m/z (CI, NH3) 201 [MH]+.
7.17 (2H, t, JH,H 7.0 Hz, m-CH(NHPh)); dC (75.5 MHz, C6D6, 25 °C)
3
26.4 (s, CH2(Cy)), 26.8 (d, JC,P 10.5 Hz, CH2(Cy)), 27.1 (d, JC,P
12.5 Hz, CH2(Cy)), 28.5 (s, CH2(COD)), 28.9 (d, JC,P 3.0 Hz, CH2(Cy)),
30.2 (s, CH2(COD)), 31.3 (d, 1JC,P 16.5 Hz, CH(Cy)), 32.8 (d, JC,P 3.0 Hz,
4.4.2. Cy2PCH3
MeLi (0.625 mL, 1 mmol), 1b (283 mg, 1 mmol) gave with MeI
(0.062 mL, 1 mmol) the dicyclohexylmethyl phosphine in 92%
(195 mg). dH (300 MHz, C6D6, 25 °C) 0.82 (3H, d, JP,H 16.5 Hz,
1
1
CH2(Cy)), 60.1 (d, JC,P 40.0 Hz, PCH2), 65.5 (d, JC,Rh 11.5 Hz,
2
1
2
CH(COD)), 98.1 (dd, JC,Rh 10.5 Hz, JC,P 7.0 Hz, CH(COD)), 113.4 (s,
o-CH(NHPh)), 114.2 (s, p-CH(NHPh)), 129.0 (s, m-CH(NHPh)),
CH3), 0.93–1.99 (22H, m, CH2, and CH(Cy)); dC (75.5 MHz, C6D6,
1
3
25 °C) 13.0 (d, JP,C 12.0 Hz, CH3), 25.5–30.0 (CH2(Cy)), 37.5 (d,
147.0 (d, JC,P 8.0 Hz, , Cipso-(NHPh)); dP (121.5 MHz, C6D6, 25 °C)
1
1JP,C 12.5 Hz, CH(Cy)); dP (121.5 MHz, C6D6, 25 °C) ꢀ19.8; m/z (CI,
ꢀ35.2 (d, JRh,P 127.5 Hz); dLi (116.6 MHz, toluene d8, 25 °C)
NH3) 213 [MH]+.
ꢀ0.66 (bs).
4.4.3. Ph2P(S)CH3
4.5.2. (Cy2PCH2NHPh)Rh(COD)Cl (5)
MeLi (0.625 mL, 1 mmol), 2a (315 mg, 1 mmol) or 2c (323 mg,
1 mmol) gave with MeI (0.062 mL, 1 mmol) the diphenylmethyl-
thiophosphorane in respectively, 90% (209 mg) and 88% (204 mg)
[RhCODCl]2 (98.5 mg, 0.2 mmol) was added to a solution of 1d
(121 mg, 0.4 mmol) in dichloromethane (5 mL). The mixture was
stirred at room temperature for 30 min. Then, the solvent was re-
moved under vacuum. The product was precipitated in hexanes
(mixture of isomers), filtered-off, and washed with hexanes
(5 mL). After drying, 5 was obtained as a yellow solid (188.9 mg,
86%). Crystals were obtained by slow diffusion of hexanes in satu-
rated dichloromethane solution of 5. Found: C, 59.28, H, 7.56, N,
2.23%. C27H42ClNPRh requires C, 58.97; H, 7.70; N 2.55%; dH
(300 MHz, C6D6, 25 °C) 0.99–1.55 (10H, m, CH2(Cy)), 1.64 (8H, m,
CH2(Cy)), 1.87 (4H, m, CH and CH2(Cy)), 2.06 (4H, m, CH2(COD)),
2
yield. dH (300 MHz, C6D6, 25 °C) 2.27 (3H, d, JP,H 13.0 Hz, CH3),
3
3
7.47 (6H, m, m- and p-CH(PPh)), 7.81 (4H, dd, JP,H 13.5 Hz JH,H
1
7.5 Hz, o-CH(PPh)); dC (75.5 MHz, C6D6, 25 °C): 21.7 (d, JP,C
60.0 Hz, CH3), 128.6 (d, JP,C 12.0 Hz, m-CH(PPh)), 130.7 (d, JP,C
2
2
4
10.5 Hz, o-CH(PPh)), 131.4 (d, JP,C 3.0 Hz, p-CH(PPh)), 133.9 (d,
1JP,C 82.5 Hz, Cipso-(PPh)); dP (121.5 MHz, C6D6, 25 °C) +35.5; m/z
(CI, NH3) 233 [MH]+.
2
4.4.4. Cy2P(S)CH3
2.18 (4H, m, CH2(COD)), 3.37 (t, JP,H = 3JH,H 5.0 Hz, PCH2), 3.63
3
MeLi (0.625 mL, 1 mmol), 2b (316 mg, 1 mmol) or 2d (336 mg,
1 mmol) gave with MeI (0.062 mL, 1 mmol) the dicyclohexylmeth-
ylthiophosphorane in respectively, 84% (205 mg) and 87% (213 mg)
yield. dH (300 MHz, C6D6, 25 °C) 0.99 (2H, m, CH2(Cy)), 1.06 (3H, d,
2JP,H 11.5 Hz, CH3), 1.19–2.02 (20H, m, CH and CH2(Cy)); dC
(2H, m, CH(COD)), 4.84 (1H, t, JH,H 5.0 Hz, NH), 5.67 (2H, m,
3
3
CH(COD)), 6.67 (2H, d, JH,H 7.5 Hz, o-CH(NHPh)), 6.75 (1H, t, JH,H
7.5 Hz, p-CH(NHPh)), 7.17 (2H, m, m-CH(NHPh)); dC (75.5 MHz,
C6D6, 25 °C) 26.6 (s, CH2(Cy)), 27.5 (d, JC,P 9.5 Hz, CH2(Cy)), 27.7
(d, JC,P 11.5 Hz, CH2(Cy)), 28.6 (s, CH2(COD)), 29.7 (s, CH2(Cy)),
30.0 (s, CH2(Cy)), 30.5 (s, CH2(Cy)), 30.4 (s, CH2(Cy)), 30.9 (s,
1
(75.5 MHz, C6D6, 25 °C) 12.9 (d, JP,C 49.5 Hz, CH3), 25.5–30.0
1
1
(CH2(Cy)), 37.5 (d, JP,C 50.5 Hz, CH(Cy)); dP (121.5 MHz, C6D6,
CH2(Cy)), 33.6 (s, CH2(COD)), 34.0 (d, JC,P 19.5 Hz, CH(Cy)), 35.9
25 °C) +54.7; m/z (CI, NH3) 245 [MH]+.
(dd, JC,P 18.0 Hz, JC,Rh 46.5 Hz, PCH2), 68.2 (d, JC,Rh 14.0 Hz,
2
1
1
2
CH(COD)), 104.1 (dd, JC,Rh 12.0 Hz, JC,P 7.0 Hz, CH(COD)), 113.9
(s, o-CH(NHPh)), 118.5 (s, p-CH(NHPh)), 129.6 (s, m-CH(NHPh)),
149.0 (d, JC,P 8.5 Hz, Cipso-(NHPh)); dP (121.5 MHz, C6D6, 25 °C)
4.4.5. Cy2PCH2NLiPh (3d)
3
MeLi (625
lL, 1 mmol) was added to a solution of amino-phos-
1
phine 1d (303 mg, 1 mmol) in toluene (3 mL) cooled at ꢀ78 °C.
After evaporation under vacuum, the product was precipitated in
5 mL of hexane, filtered-off under nitrogen, and dried under vac-
uum. Amido anion 3d was obtained as a white solid (323.3 mg,
96%). Crystals of this product were obtained by slow evaporation
of diethyl ether in the glove box. NMR analyses were performed
on in situ generated anion. dH (300 MHz, C6D6, 25 °C) 1.19–1.44
(10H, m, CH2(Cy)), 1.64 (2H, m, CH(Cy)), 1.71 (6H, m, CH2(Cy)),
+24.0 (d, JP, Rh 145.5 Hz).
4.5.3. [(Cy2PCH2NHPh)RhCOD][Barf4] (6-Barf4)
NaBarf4 (88.6 mg, 0.1 mmol) was added to a dichloromethane
solution (4 mL) of 5 (55 mg, 0.2 mmol). The mixture was stirred
at room temperature for 30 min. Then, NaCl salt was eliminated
by filtration under nitrogen and the filtrate was evaporated under
vacuum. The result product was precipitated in hexanes (mixture
of isomers), filtered-off, and washed with hexanes (5 mL). After
drying 6-Barf4 was obtained as an orange solid (116 mg, 84%).
Found: C, 51.13, H, 4.18, N, 0.85%. C59H54BF24NPRh requires C,
51.44; H, 3.95; N, 1.02; dH (300 MHz, CD2Cl2, 25 °C) 1.17–1.93
(22H, m, CH and CH2(Cy)), 2.12 (4H, m, CH2(COD)), 2.33 (4H, m,
3
1.95 (4H, m, CH2(Cy)), 3.53 (2H, bs, PCH2), 6.55 (1H, t, JH,H
3
7.5 Hz, p-CH(NHPh)), 6.81 (2H, d, JH,H 7.5 Hz, o-CH(NHPh)), 7.31
3
(2H, t, JH,H 7.5 Hz, m-CH(NHPh)); dC (75.5 MHz, C6D6, 25 °C) 26.9
(s, CH2(Cy)), 27.8 (t, JC,P 6.5 Hz, CH2(Cy)), 30.5 (d, JC,P 10.5 Hz,
1
2
CH2(Cy)), 33.6 (d, JC,P 11.5 Hz, CH(Cy)), 44.9 (d, JC,P 4.5 Hz,
PCH2), 111.9 (s, o-CH(NHPh)), 113.1 (s, p-CH(NHPh)), 130.0 (s, m-
3
CH2(COD)), 3.70 (1H, t, JH,H 8.0 Hz, NH), 4.14 (2H, m, CH(COD)),
3
2
3
CH(NHPh)), 161.4 (d, JC,P 17.0 Hz, Cipso-(NHPh)); dP (121.5 MHz,
4.33 (2H, m, CH(COD)), 4.75 (2H, dd, JP,H 5.0 Hz, JH,H 8.0 Hz,
3
3
C6D6, 25 °C) ꢀ6.8; dLi (116.6 MHz, toluene d8, 25 °C) +1.74 (bs).
PCH2), 7.02 (2H, d, JH,H 7.5 Hz, o-CH(NHPh)), 7.10 (1H, t, JH,H
7.5 Hz, p-CH(NHPh)), 7.32 (2H, t, JH,H 7.5 Hz, m-CH(NHPh)), 7.47
3
4.5. Coordination experiments
(4H, bs, p-CH(Barf4), 7.64 (8H, bs, o-CH(Barf4)); dC (75.5 MHz,
CD2Cl2, 25 °C) 24.9 (s, CH2(Cy)), 25.5 (d, JC,P 10.5 Hz, CH2(Cy)),
25.8 (d, JC,P 13.5 Hz, CH2(Cy)), 27.0 (s, CH2(COD)), 27.9 (s, CH2(COD),
28.4 (d, JC,P 3.0 Hz, CH2(Cy)), 30.9 (dd, JC,Rh 17.0 Hz , JC,P 39.0 Hz,
4.5.1. (Cy2PCH2NLiPh)RhCODCl (4)
[RhCODCl]2 (49.3 mg, 0.1 mmol) was added to a solution 3d
(62.0 mg, 0.2 mmol) in toluene (3 mL). The reaction mixture was
stirred at room temperature for 30 min, and then the solvent was
evaporated under vacuum. The product was precipitated in hex-
anes (mixture of isomers), filtered-off, and washed with hexanes
(5 mL). After drying, 4 was obtained as a red solid (98 mg, 88%).
dH (300 MHz, C6D6, 25 °C) 1.01 (6H, m, CH2(Cy)), 1.19 (2H, m,
CH2(Cy)), 1.65 (12H, m, CH2(Cy)), 1.87 (2H, m, CH(Cy)), 1.95 (4H,
m, CH2(COD)), 2.26 (4H, m, CH2(COD)), 3.78 (2H, m, CH(COD)),
2
1
2
CH(Cy)), 59.7 (dd, JC,Rh 4.5 Hz, JC,P 29.0 Hz, PCH2), 75.3 (dd, JC,P
1
12.5 Hz, JC,Rh 70 Hz, CH(COD)), 104.9 (m, CH2(COD)), 118.0 (quin-
3
tuplet, JC,F 3.5 Hz, p-CH(Barf4)), 119.0 (s, o-CH(NHPh)), 125.1 (q,
3
1JC,F 272 Hz, CF3(Barf4)), 126.9 (s, p-CH(NHPh)), 129.5 (qq, JC,B
2
31.5 Hz, JC,F 2.5 Hz, m-CH(Barf4)), 131.4 (s, m-CH(NHPh)), 135.3
3
1
(s, o-CH(Barf4)), 146.5 (d, JC,P 8.0 Hz, Cipso-(NHPh)), 162.3 (d, JC,B
1
50.0 Hz, Cipso-(Barf4)); dP (121.5 MHz, C6D6, 25 °C) -20.1 (d, JP,Rh
126.5 Hz).