V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
2093
2
solid, which was washed with a mixture diethyl ether/
hexanes (3 · 30 ml; 1:1 v/v) and dried in vacuo. (3a):
Yield: 54% (0.209 g); Anal. Calcd for RuC59H55F6-
P5O4N2S2 Æ 1/5CH2Cl2 (1307.13 g molꢀ1): C, 54.40; H,
4.27; N, 2.14. Found: C, 54.48; H, 4.18; N, 2.17%; Con-
ductivity (acetone, 20 ꢁC) 107 Xꢀ1 cm2 molꢀ1; IR (KBr)
m = 557 (m), 689 (m), 729 (w), 768 (w), 842 (s), 919 (s),
1024 (w), 1111 (m), 1130 (m), 1161 (m), 1191 (s), 1287
(w), 1438 (m), 1488 (s), 1570 (m), 2860 (w), 2960 (w)
Hz, OCH2CH3), 64.24 (d, JCP = 7.5 Hz, OCH2CH3),
79.09, 82.18, 83.32 and 84.19 (s, CH of p-cymene),
99.60 and 110.67 (s, C of p-cymene), 125.25–135.56
(m, Ph) ppm.
4.5. Synthesis of [Ru(g6-p-cymene)(j2-C,N-
C[P{@NP(@S)(OR)2}Ph2]2)] (R = Ph (4a),
Et (4b))
cmꢀ1
;
31P{1H} NMR (CD2Cl2) d = 28.49 (ddd,
A solution of the corresponding cationic complex
[Ru(g6-p-cymene)(j3-C,N,S-CH[P{@NP(@S)(OR)2}-
Ph2]2)][PF6] 3a,b (0.1 mmol) in 30 ml of THF was trea-
ted, at room temperature, with NaH (0.024 g, 1 mmol)
for 3 h. The solvent was then removed under vacuum,
the crude product extracted with diethyl ether (ca.
50 ml), and the extract filtered. Concentration of the
resulting solution (ca. 2 ml) followed by the addition
of hexanes (ca. 50 ml) precipitated a violet solid, which
was filtered, washed with hexanes (3 · 20 ml) and dried
in vacuo. (4a): Yield: 80% (0.092 g); Anal. Calcd for Ru-
C59H54O4P4N2S2 (1144.17 g molꢀ1): C, 61.93; H, 4.76;
N, 2.45. Found: C, 62.00; H, 4.48; N, 2.20%; IR (KBr)
m = 498 (w), 531 (w), 617 (w), 688 (s), 768 (m), 804 (s),
909 (m), 1024 (s), 1101 (s), 1159 (m), 1195 (s), 1261
(s), 1434 (m), 1488 (s), 1590 (m), 2924 (w), 2962 (w),
2JPP = 18.6 and 4.7 Hz, JPP = 3.1 Hz, Ph2P@N), 43.08
(d, 2JPP = 18.6 Hz, (PhO)2P@SARu), 60.65 (dd,
2JPP = 27.6 and 4.7 Hz, Ru–N@PPh2), 66.89 (dd,
4
2JPP = 27.6 Hz, 4JPP = 3.1 Hz, Ru–NP(@S)(OPh)2)
ppm; 1H NMR (CD2Cl2) d = 0.83 (d, 3H, JHH
=
3
3
6.9 Hz, CH(CH3)2), 1.04 (d, 3H, JHH = 6.7 Hz, CH-
(CH3)2), 1.90 (s, 3H, CH3), 2.16 (m, 1H, CH(CH3)2),
2
4.21 (dd, 1H, JHP = 11.8 and 7.9 Hz, PCHP), 4.31
3
and 4.59 (d, 1H each, JHH = 5.8 Hz, CH of p-cymene),
5.40 (br, 2H, CH of p-cymene), 6.70–8.32 (m, 40H, Ph)
1
ppm; 13C{1H} NMR (CD2Cl2) d = ꢀ8.16 (dddd, JCP
=
3
55.7 and 55.7 Hz, JCP = 17.8 and 10.9 Hz, PCHP),
18.24 (s, CH3), 19.93 and 23.26 (s, CH(CH3)2), 30.45
(s, CH(CH3)2), 77.43, 82.17, 83.24 and 84.45 (s, CH of
p-cymene), 98.14 and 113.84 (s, C of p-cymene),
2
120.02–135.22 (m, Ph), 151.05 (d, JCP = 12.1 Hz, Cipso
2
of OPh), 151.12 (d, JCP = 7.6 Hz, Cipso of OPh),
3047 (w) cmꢀ1
;
31P{1H} NMR (C6D6) d = 12.72 (ddd,
2JPP = 96.7 and 27.0 Hz, JPP = 9.8 Hz, Ph2P@N),
4
2
2
151.34 (d, JCP = 6.8 Hz, Cipso of OPh), 152.10 (d,
47.71 (d, JPP = 27.0 Hz, (PhO)2P@S), 61.00 (dd,
2JCP = 8.3 Hz, Cipso of OPh) ppm. (3b): Yield: 49%
(0.161 g); Anal. Calcd for RuC43H55F6P5O4N2S2
(1097.98 g molꢀ1): C, 47.04; H, 5.05; N, 2.55. Found:
C, 47.33; H, 5.21; N, 2.53%; Conductivity (acetone,
20 ꢁC) 120 Xꢀ1 cm2 molꢀ1; IR (KBr) m = 487 (w), 531
(w), 557 (s), 596 (w), 655 (w), 691 (m), 752 (s), 840 (s),
912 (m), 958 (s), 1026 (s), 1110 (s), 1159 (m), 1264 (m),
1285 (m), 1388 (w), 1438 (s), 1473 (w), 1588 (w), 2901
2JPP = 23.0 Hz, 4JPP = 9.8 Hz, Ru–NP(@S)(OPh)2),
2
66.02 (dd, JPP = 96.7 and 23.0 Hz, Ru–N@PPh2)
ppm; 1H NMR (C6D6) d = 1.11 (d, 6 H, JHH = 6.9
3
Hz, CH(CH3)2), 1.96 (s, 3H, CH3), 2.24 (sept, 1H,
3JHH = 6.9 Hz, CH(CH3)2), 5.48 and 5.59 (d, 2H each,
3JHH = 5.9 Hz, CH of p-cymene), 6.85–7.90 (m, 40H,
Ph) ppm; 13C{1H} NMR (C6D6) d = 19.33 (s, CH3),
23.46 (s, CH(CH3)2), 31.34 (s, CH(CH3)2), 79.11 and
81.97 (s, CH of p-cymene), 87.17 and 98.69 (s, C of p-
cymene), 121.61–136.44 (m, Ph and PCP), 153.32 (d,
2JCP = 9.3 Hz, Cipso of OPh) ppm. (4b): Yield: 83%
(0.079 g); Anal. Calcd for RuC43H54O4P4N2S2 (952.00
g molꢀ1): C, 54.25; H, 5.72; N, 2.94. Found: C, 54.01;
H, 5.61; N, 2.89%; IR (KBr) m = 479 (w), 531 (w), 556
(w), 690 (m), 748 (m), 801 (s), 911 (w), 948 (m), 1024
(s), 1102 (s), 1152 (m), 1261 (s), 1387 (w), 1436 (m),
(w), 2928 (w), 2978 (m), 3059 (w) cmꢀ1
;
31P{1H}
2
NMR ((CD3)2CO) d = 26.27 (ddd, JPP = 17.8 and
4
2
3.4 Hz, JPP = 5.1 Hz, Ph2P@N), 51.29 (d, JPP
=
2
17.8 Hz, (EtO)2P@SARu), 64.68 (dd, JPP = 23.8 and
2
3.4 Hz, Ru–N@PPh2), 69.80 (dd, JPP = 23.8 Hz,
4JPP = 5.1 Hz, Ru–NP(@S)(OEt)2) ppm; 1H NMR
3
((CD3)2CO) d = 1.15 and 1.50 (t, 3H each, JHH
=
7.0 Hz, OCH2CH3), 1.21–1.28 (m, 12H, CH(CH3)2 and
OCH2CH3), 2.15 (s, 3H, CH3), 3.06 (m, 1H, CH(CH3)2),
3.65, 3.87 and 4.03 (m, 2H each, OCH2CH3), 4.30 (m,
3H, OCH2CH3 and PCHP), 4.64 and 5.39 (d, 1H each,
3JHH = 5.6 Hz, CH of p-cymene), 5.06 (br, 2H, CH of p-
cymene), 7.17–8.44 (m, 20H, Ph) ppm; 13C{1H} NMR
1460 (w), 2855 (w), 2931 (w), 2951 (w) cmꢀ1
;
31P{1H}
2
NMR (C6D6) d = 11.59 (ddd, JPP = 84.7 and 29.3 Hz,
4JPP = 9.8 Hz, Ph2P@N), 55.44 (d, JPP = 29.3 Hz,
2
2
(EtO)2P@S), 60.49 (dd, JPP = 84.7 and 14.7 Hz, Ru–
2
4
N@PPh2), 70.23 (dd, JPP = 14.7 Hz, JPP = 9.8 Hz,
1
((CD3)2CO) d = ꢀ8.09 (dddd, JCP = 62.4 and 62.4 Hz,
Ru–NP(@S)(OEt)2) ppm; 1H NMR (C6D6) d = 1.01
and 1.21 (t, 6H each, JHH = 6.9 Hz, OCH2CH3), 1.16
3
3
3JCP = 17.2 and 10.6 Hz, PCHP), 15.96 (d, JCP = 5.2
3
Hz, OCH2CH3), 16.01 (d, JCP = 6.0 Hz, OCH2CH3),
3
(d, 6H, JHH = 6.9 Hz, CH(CH3)2), 2.10 (s, 3H, CH3),
3
16.07 and 16.12 (d, JCP = 4.8 Hz, OCH2CH3), 18.21
(s, CH3), 21.25 and 22.33 (s, CH(CH3)2), 30.62 (s,
3
2.61 (sept, 1H, JHH = 6.9 Hz, CH(CH3)2), 4.04 (m,
3
8H, OCH2CH3), 5.41 and 5.47 (d, 2H each, JHH = 5.4
2
CH(CH3)2), 63.51 (d, JCP = 8.5 Hz, OCH2CH3), 63.60
Hz, CH of p-cymene), 6.94–7.94 (m, 20H, Ph) ppm;
13C{1H} NMR (C6D6) d = 15.98 and 16.29 (d,
2
(d, JCP = 10.0 Hz, OCH2CH3), 63.65 (d, JCP = 5.2
2