210
M. Pošta et al. / Inorganica Chimica Acta 362 (2009) 208–216
2
2
31P NMR (CD2Cl2, ꢂ30 °C): dP1 = 60.1
d
(1JRhP = 107.6 Hz),
2.56 m (2H, CH, i-Pr), 3.22 dd (1H, JHH = 16.0 Hz, JPH = 11.7 Hz,
2
2
dP2 = 65.7 d (1JRhP = 120.1 Hz).
CH2, PCH2), 3.24 dd (1 H, JHH = 16.0 Hz, JPH = 11.7 Hz, CH2), 3.64
1H NMR (CD2Cl2, ꢂ30 °C): 1.30 s (9H, t-Bu), 1.31 s (9H, t-Bu),
1.42–2.13 bm (CH2, c-C6H11), 2.41–2.50 bm (CH2, c-C6H11), 2.86–
2.87 bm (CH2, c-C6H11), 3.16–3.25 m (CH2, c-C6H11), 3.23–3.41 m
(CH, c-C6H11), 3.32–3.38 m (1H, CH2, PCH2), 3.55–3.72 m (CH,
c-C6H11), 3.81–3.89 m (1H, CH2, PCH2), 4.11 dd (1H, 2JHH = 23.5 Hz,
2JPH = 11.7 Hz, CH2, PCH2), 4.74 dd (1H, 2JHH = 17.0 Hz,
2JPH = 10.2 Hz, CH2, PCH2).
d sep (2H, JPH = 14.4 Hz, JHH = 7.2 Hz, CH, i-Pr), 4.23 d sep (2H,
2
3
2JPH = 14.9 Hz, JHH = 7.5 Hz, CH, i-Pr), 4.57 dd (1H, JHH = 17.9 Hz,
3
2
2JPH = 9.3 Hz, CH2).
13C NMR (CDCl3): 17.77 s (CH3, i-Pr), 18.94 s (CH3, i-Pr), 19.57d
(2JPC = 7.3 Hz, CH3, i-Pr), 20.19–20.57 m (3ꢃ CH3, i-Pr), 20.32 s
(CH3, i-Pr), 21.19 d (1JPC = 19.8 Hz, CH2, PCH2), 21.63 s (CH3, i-Pr),
26.57 d (1JPC = 15.0 Hz, CH, i-Pr), 27.73 s (CH3, t-Bu), 28.20 s (CH3,
t-Bu), 29.53 d (1JPC = 27.9 Hz, CH, i-Pr), 31.20 d (1JPC = 29.1 Hz, CH,
i-Pr), 33.58 d (1JPC = 20.4 Hz, CH, i-Pr), 34.69 d (1JPC = 31.4 Hz, CH2,
PCH2), 40.63 d (3JPC = 2.3 Hz, C, t-Bu), 41.11 d (3JPC = 6.6 Hz, C,
t-Bu), 174.00 d (2JPC = 2.0 Hz, C, C@N), 185.62 s (C, C@N).
13C NMR (CD2Cl2, ꢂ30 °C): 22.20 d (1JPC = 19.9 Hz, CH2, PCH2),
26.49–26.63 m (CH2), 28.97–35.37 m (CH2, c-C6H11), 30.93 s
(CH3, t-Bu), 31.48 s (CH3, t-Bu), 37.54 d (1JPC = 31.2 Hz, CH2,
PCH2), 37.54 d (1JPC = 31.2 Hz, CH, c-C6H11), 40.67 d (1JPC = 14.1 Hz,
CH, c-C6H11), 42.53
d d
(1JPC = 25.2 Hz, CH, c-C6H11), 43.63
(3JPC = 2.2 Hz, C, t-Bu), 43.95 d (3JPC = 6.4 Hz, C, t-Bu), 47.17–
47.62 m (CH, c-C6H11), 176.22 s (C, C@N), 188.16 s (C, C@N).
31P NMR spectra simulation [8] parameters describing the ex-
change 13–13a–14.
2.2.5. mer-½RhCl3fBut PCH2CðButÞ@NN@CðButÞCH2PBut gꢁ (16)
2
2
Complex was prepared by method A, monocrystal suitable for
X-ray diffraction was obtained by slow diffusion of hexane vapour
to a chloroform solution at room temperature.
ꢂ30 °C: Complex 13, dP1 = 60.1 (1JRhP = 107.9 Hz), dP2 = 65.7
31P NMR (CDCl3): ABX 10.8 (1JRhP = 85.9 Hz), 57.4
(1JRhP = 86.0 Hz) (2JPP = 528.0 Hz).
2
(1JRhP = 120.4 Hz), JPP = 4.6 Hz, relative concentration 1; complex 13a,
dP1 = 62.8 (1JRhP = 109.0 Hz), dP2 = ꢂ4.7 (1JRhP = 0 Hz), 2JPP = 0 Hz, rel-
1H NMR (CDCl3) (ꢂ30 °C): 1.31 s (9H, t-Bu), 1.35 s (9H, t-Bu),
ative concentration 0.0095; complex 14, dP1 = 41.5 (1JRhP = 84.8 Hz),
1.45 s (9H, t-Bu), 1.49 s (9H, t-Bu), 1.65 d (9H, J = 14.3 Hz, t-Bu),
2
2
dP2 = 40.8 (1JRhP = 86.8 Hz), JPP = 545 Hz, relative concentration
1.71
d
(9H, J = 14.4 Hz, t-Bu), 2.48 ddd (1H, JHH = 18.0 Hz,
0.11. Exchange rates, r1 (13–13a) 135 sꢂ1, r2 (13a–14) 2030 sꢂ1
.
2JPH = 13.2 Hz, 4JPH = 7.5 Hz, CH2, PCH2), 3.37 ddd (1H,
25 °C: Complex 13, dP1 = 57.0 (1JRhP = 119.3 Hz), dP2 = 62.9
2JHH = 18.5 Hz, JPH = 11.6 Hz, JPH = 7.7 Hz, CH2, PCH2), 3.51 dd
2
4
2
2
2
2
(1JRhP = 123.9 Hz), JPP = 4.5 Hz, relative concentration 1; complex
(1H, JHH = 18.0 Hz, JPH = 9.0 Hz, CH2), 4.28 dd (1H, JHH = 18.8 Hz,
13a, dP1 = 70.0 (1JRhP = 109.5 Hz), dP2 = 0.7 (1JRhP = 0 Hz), JPP = 0 Hz,
2JPH = 5.2 Hz, CH2, PCH2).
2
relative
concentration
0.023;
complex
14,
dP1 = 41.5
13C NMR (CDCl3): 16.75 d (1JPC = 16.4 Hz, CH2, PCH2), 29.32 s
(CH3, t-Bu), 29.48 s (CH3, t-Bu), 31.58 broad s (CH3, t-Bu), 31.76
(1JRhP = 84.8 Hz), dP2 = 40.8 (1JRhP = 86.8 Hz), JPP = 545 Hz, relative
concentration 0.13. Exchange rates, r1 (13–13a) 5900 sꢂ1, r2
2
broad s (CH3, t-Bu), 37.45 dd (1JPC = 19.1 Hz, JPC = 3.0 Hz, CH2,
3
(13a–14) 3.02 ꢃ 1016 sꢂ1
.
PCH2), 38.85–39.47 m (C, t-Bu), 41.38–41.78 m (C, t-Bu),
43.64 d (3JPC = 4.7 Hz, C, t-Bu), 43.87 d (3JPC = 4.8 Hz, C, t-Bu),
2.2.3. mer-[RhCl3{(C6H11)2PCH2C(But)@NN@C(But)CH2P(C6H11)2}] (14)
Complex was prepared by method B, in the manner described
above. A monocrystal suitable for the X-ray diffraction was se-
lected from the crystalline product obtained by method B.
173.25 s (C, C@N), 197.46 dd (2JPC = 4.9 Hz, JPC = 1.5 Hz, C,
4
C@N).
2.2.6. fac-[IrCl3{Ph2PCH2C(But)@NN@C(But)CH2PPh2}] (17)
Complex was prepared by method B.
31P NMR (CDCl3): ABX 40.8 (1JRhP = 86.8 Hz), 41.5 (1JRhP
84.8 Hz) (2JPP = 545.0 Hz).
=
31P NMR (CDCl3): dP1 = ꢂ8.3 d, dP2 = 30.0 d (2JPP = 21.3 Hz).
1H NMR (CDCl3): 0.99 s (9H, t-Bu), 1.45 s (9H, t-Bu), 4.23 d (1H,
2JPH = 9.5 Hz, CH2, PCH2), 4.30 d (1H, 2JPH = 9.3 Hz, CH2, PCH2), 4.39
1H NMR (CDCl3): 1.21 s (9H, CH3, t-Bu), 1.24 s (9H, CH3, t-Bu),
1.44–1.53 m (CH2, c-C6H11), 1.70–1.88 m (CH2, c-C6H11), 2.05–
2
2
2
2.09 m (CH2, c-C6H11), 2.46 d (2H, JPH = 5.8 Hz, CH2, PCH2), 2.52
d (1H, JPH = 5.7 Hz, CH2, PCH2), 4.48 d (1H, JPH = 6.0 Hz, CH2,
PCH2), 6.74–6.80 m (2H, CH, Ph), 6.97–7.07 m (4H, CH, Ph), 7.16–
7.21 m (2H, CH, Ph), 7.31–7.74 m (14H, CH, Ph).
broad s (CH2, c-C6H11), 2.72–2.78 m (2H, CH, c-C6H11), 2.81–2.86
m (CH2, c-C6H11), 2.97–3.04 m (2H, CH, c-C6H11), 3.67 d (2H,
2JPH = 4.0 Hz, CH2, PCH2).
13C NMR (CDCl3): 25.87 d (1JPC = 17.1 Hz, CH2, PCH2), 27.83 s
(CH3, t-Bu), 28.81 s (CH3, t-Bu), 39.98 d (3JPC = 2.0 Hz, C, t-Bu),
13C NMR (CDCl3): 19.36 dd (1JPC = 6.4 Hz, JPC = 4.0 Hz, CH2,
3
PCH2), 26.60 s (CH2, c-C6H11), 26.82 s (CH2, c-C6H11), 27.50–28.19
m (CH2, c-C6H11) 28.14 s (CH3, t-Bu), 28.33 s (CH3, t-Bu), 29.52 d
(J = 2.5 Hz, CH2, c-C6H11), 29.66 s (CH2, c-C6H11), 30.40 d (J =
40.62 d
(3JPC = 5.8 Hz, C, t-Bu), 45.21 dd (1JPC = 32.3 Hz,
3JPC = 2.6 Hz, CH2, PCH2), 128.41–129.80 m (CH, Ph), 130.51–
131.23 m (CH, Ph), 132.02 d (1JPC = 4.9 Hz, C, Ph), 133.06 d
(1JPC = 6.0 Hz, C, Ph), 133.36–133.52 m (CH, Ph), 133.55 d
(1JPC = 9.6 Hz, C, Ph), 134.04 d (1JPC = 4.9 Hz, C, Ph), 174.14 s
(C, C@N), 184.23 dd (J = 7.0 Hz, J = 2.7 Hz, C, C@N).
3.9 Hz, CH2, c-C6H11), 30.50 s (CH2, c-C6H11), 34.73 dd (1JPC
=
3
14.8 Hz, JPC = 7.1 Hz, CH2, PCH2), 35.86 dd (1JPC = 10.1 Hz,
3JPC = 7.7 Hz, CH, c-C6H11), 36.11 dd (1JPC = 11.2 Hz, JPC = 8.9 Hz,
3
CH, c-C6H11), 41.32 s (C, t-Bu), 41.45 broad s (C, t-Bu),
173.13 s (C, C@N), 189.17 dd (2JPC = 4.1 Hz, JPC = 4.0 Hz, C,
2.2.7. fac-[IrCl3{(C6H11)2PCH2C(But)@NN@C(But)CH2P(C6H11)2}] (18)
Complex was prepared by method B.
4
C@N).
31P NMR (CDCl3): dP1 = 7.0 d, dP2 = 18.9 d (2JPP = 20.4 Hz).
1H NMR (CDCl3): 1.22 broad s (18H, t-Bu), 1.24–1.36 m (CH2, c-
2.2.4. fac-½RhCl3fPri PCH2CðButÞ@NN@CðButÞCH2PPri gꢁ (15)
2
2
2
Complex was prepared both by method A and by method B. A
monocrystal suitable for the X-ray analysis was obtained by a slow
evaporation of the solvent at room temperature.
C6H11), 1.61–2.14 m (CH2, c-C6H11), 3.88 d (1H, JPH = 2.8 Hz, CH2,
PCH2), 4.01 broad s (1H, CH2, PCH2), 4.84 broad s (1H, CH2,
PCH2), 5.56 d (1H, JPH = 2.8 Hz, CH2, PCH2).
2
31P NMR (CDCl3): dP1 = 64.1 dd (1JRhP = 109.6 Hz, JPP = 11.5 Hz),
13C NMR (CDCl3): 22.55 d (1JPC = 15.3 Hz, CH2, PCH2), 25.97–
32.03 m (CH2, c-C6H11), 28.05 s (CH3, t-Bu), 31.20 s (CH3, t-Bu),
33.90 d (1JPC = 11.8 Hz, CH2, PCH2), 39.72 d (1JPC = 2.0 Hz, CH, c-
C6H11), 43.57 d (1JPC = 1.8 Hz, CH, c-C6H11), 48.02 d (1JPC = 1.9 Hz,
CH, c-C6H11), 50.44 d (1JPC = 1.2 Hz, CH, c-C6H11), 58.35 broad s
(C, t-Bu), 58.90 broad s (C, t-Bu), 174.66 broad s (C, C@N),
181.34 broad s (C, C@N).
2
2
dP2 = 64.8 dd (1JRhP = 118.5 Hz, JPP = 12.4 Hz).
2
3
1H NMR (CDCl3): 1.03 dd (3H, JPH = 14.1 Hz, JHH = 6.9 Hz, CH3,
i-Pr), 1.32 s (9H, t-Bu), 1.32 s (9H, t-Bu), 1.36–1.48 m (12 H, CH3, i-
2
3
Pr), 1.48 dd (3H, JPH = 17.8 Hz, JHH = 7.5 Hz, CH3, i-Pr), 1.53–1.61
2
3
m (1H, CH2, PCH2), 1.65 dd (3H, JPH = 17.6 Hz, JHH = 7.2 Hz, CH3,
i-Pr), 1.66 dd (3H, JPH = 16.1 Hz, JHH = 7.3 Hz, CH3, i-Pr), 2.38–
2
3