1364w, 1437m, 1483w, 1588w, 2891w, 2932w, 2976m, 3061w; dH
(CDCl3) 1.22 (t, 12H, 3J(HH) = 7.1 Hz, CH3), 4.00 (m, 8H, OCH2),
4.47 and 4.80 (br, 4H each, C5H4), 7.28–7.39 (m, 8H, Ph), 7.42–
961s, 1023vs, 1116s, 1173m, 1242vs, 1437s, 1483w, 1589w, 2899w,
2981m, 3060w; dH (CDCl3) 1.10 (t, 12H, 3J(HH) = 7.0 Hz, CH3),
3.94 (m, 8H, OCH2), 4.11 (t, 2H, 2J(HP) = 13.4 Hz, PCH2), 7.23–
3
3
7.64 (m, 12H, Ph); dC (CDCl3) 16.01 (d, J(CP) = 8.5 Hz, CH3),
7.65 (m, 20H, Ph); dC (CDCl3) 15.66 (d, J(CP) = 8.7 Hz, CH3),
61.86 (d, 2J(CP) = 6.3 Hz, OCH2), 72.90 (dd, 1J(CP) = 122.1 Hz,
22.73 (tt, J(CP) = 71.2 Hz, J(CP) = 5.7 Hz, PCH2), 64.10 (d,
2J(CP) = 7.0 Hz, OCH2), 127.23 (dd, 1J(CP) = 107.1 Hz, 3J(CP) =
1
3
3
3J(CP) = 2.2 Hz, C of C5H4), 74.27 (d, J(CP) = 13.8 Hz, CH
2
3
of C5H4), 74.96 (d, J(CP) = 10.8 Hz, CH of C5H4), 128.08 (d,
2.3 Hz, i-Ph), 129.06 (d, J(CP) = 12.8 Hz, m-Ph), 131.60 (d,
3J(CP) = 13.0 Hz, m-Ph), 130.66 (dd, 1J(CP) = 109.8 Hz, 3J(CP) =
3.7 Hz, i-Ph), 131.96 (s, p-Ph), 132.00 (d, 2J(CP) = 10.8 Hz, o-Ph).
5b. Yield: 0.919 g, 85% (Found: C, 64.37; H, 4.59; N, 2.70.
FeC58H48O4P4N2S2 requires C, 64.45; H, 4.48; N, 2.59%); mmax/cm−1
(KBr) 486w, 481m, 523w, 555m, 634w, 687s, 743s, 774s, 830m,
880s, 910s, 1026w, 1116m, 1192s, 1210vs, 1274s, 1436m, 1481s,
1593m, 2963w, 3021w, 3047w, 3068w; dH (CDCl3) 4.34 and 4.60
(br, 4H each, C5H4), 7.12–7.34 (m, 20H, Ph), 7.41–7.58 (m, 20H,
Ph); dC (CDCl3) 72.40 (dd, 1J(CP) = 122.5 Hz, 3J(CP) = 3.3 Hz,
2J(CP) = 10.9 Hz, o-Ph), 133.24 (s, p-Ph); MS (FAB) m/z 827.9
(100%) [M+ + 1].
7b. Yield: 0.520 g, 83% (Found: C, 46.79; H, 3.43; N, 2.12.
AgC49H42F6O4P4N2S2Sb requires C, 46.91; H, 3.37; N, 2.23%);
conductivity (acetone, 20 ◦C) 121 X−1 cm2 mol−1; mmax/cm−1 (KBr)
500m, 600w, 618w, 658s (SbF6−), 689s, 744m, 771s, 834w, 927s,
1006w, 1024m, 1070w, 1165m, 1171s, 1193vs, 1280s, 1437m, 1487s,
1589m, 2895w, 2940w, 3060w; dH (CD2Cl2) 4.12 (t, 2H, 2J(HP) =
13.7 Hz, PCH2), 6.94–7.57 (m, 30H, Ph); dC (CD2Cl2) 27.84 (tt,
1J(CP) = 68.7 Hz, 3J(CP) = 5.5 Hz, PCH2), 121.29 (d, 3J(CP) =
4.8 Hz, o-OPh), 125.91 (s, p-OPh), 126.63 (dd, 1J(CP) = 108.7 Hz,
3J(CP) = 3.0 Hz, i-Ph), 129.56 (d, 3J(CP) = 12.9 Hz, m-Ph), 130.19
(s, m-OPh), 132.24 (d, 2J(CP) = 10.7 Hz, o-Ph), 134.04 (s, p-Ph),
151.46 (d, 2J(CP) = 10.2 Hz, i-OPh); MS (FAB) m/z 1019.8 (30%)
[M+ + 1].
3
C of C5H4), 74.44 (d, J(CP) = 13.8 Hz, CH of C5H4), 75.41 (d,
3
2J(CP) = 11.2 Hz, CH of C5H4), 121.69 (d, J(CP) = 5.2 Hz, o-
3
OPh), 124.43 (s, p-OPh), 128.58 (d, J(CP) = 13.0 Hz, m-Ph),
129.47 (s, m-OPh), 130.14 (dd, 1J(CP) = 108.7 Hz, 3J(CP) =
2
3.7 Hz, i-Ph), 132.33 (d, J(CP) = 11.2 Hz, o-Ph), 132.63 (d,
4J(CP) = 2.6 Hz, p-Ph), 152.63 (d, 2J(CP) = 9.3 Hz, i-OPh).
6a. Yield: 0.662 g, 88% (Found: C, 47.73; H, 7.44; N, 3.84.
FeC30H56O4P4N2S2 requires C, 47.87; H, 7.50; N, 3.72%); mmax/cm−1
(KBr) 488w, 501m, 578w, 632w, 660s, 684m, 753s, 813m, 887w,
943s, 1038vs, 1096m, 1175s, 1202w, 1246s, 1315s, 1391s, 1464m,
2893m, 2935m, 2973s, 3082w; dH (CDCl3) 1.17–1.37 (m, 36H, CH3
and CH(CH3)2), 2.49 (m, 4H, CH(CH3)2), 4.11 (m, 8H, OCH2),
4.69 and 4.86 (br, 4H each, C5H4); dC (CDCl3) 16.50 (m, CH3 and
8a. Yield: 0.468 g, 87% (Found: C, 37.88; H, 4.16; N, 2.73.
AgC34H44F6O4P4N2S2Sb requires C, 37.94; H, 4.12; N, 2.60%);
conductivity (acetone, 20 ◦C) 119 X−1 cm2 mol−1; mmax/cm−1 (KBr)
520m, 586w, 658s (SbF6−), 693s, 744s, 792m, 830w, 963s, 1026vs,
1120s, 1161w, 1182m, 1261s, 1301s, 1367w, 1390w, 1439m, 1590w,
2903w, 2936w, 2983m, 3060w; dH (CDCl3) 1.23 (t, 12H, 3J(HH) =
7.1 Hz, CH3), 2.81 (br, 4H, PCH2), 4.04 (m, 8H, OCH2), 7.28–
1
3
CH(CH3)2), 26.15 (d, J(CP) = 68.5 Hz, CH(CH3)2), 61.69 (d,
7.67 (m, 20H, Ph); dC (CDCl3) 15.81 (d, J(CP) = 8.6 Hz, CH3),
2J(CP) = 6.3 Hz, OCH2), 71.39 (dd, 1J(CP) = 103.1 Hz, 3J(CP) =
20.65 (m, PCH2), 64.26 (d, 2J(CP) = 7.8 Hz, OCH2), 126.10 (dd,
1J(CP) = 105.3 Hz, 3J(CP) = 4.8 Hz, i-Ph), 129.45 (d, 3J(CP) =
3
4.4 Hz, C of C5H4), 73.54 (d, J(CP) = 11.2 Hz, CH of C5H4),
73.92 (d, 2J(CP) = 9.7 Hz, CH of C5H4).
12.9 Hz, m-Ph), 131.26 (d, J(CP) = 10.7 Hz, o-Ph), 133.67 (s,
2
p-Ph); MS (FAB) m/z 841.9 (100%) [M+ + 1].
6b. Yield: 0.869 g, 92% (Found: C, 58.23; H, 6.03; N, 3.11.
FeC46H56O4P4N2S2 requires C, 58.47; H, 5.97; N, 2.96%); mmax/cm−1
(KBr) 500m, 567w, 599w, 659s, 689s, 729m, 772s, 812m, 887s,
910s, 1025w, 1043w, 1174m, 1200vs, 1251w, 1323s, 1391w, 1488s,
1591s, 2873w, 2934w, 2966m, 3073w; dH (CDCl3) 1.17 (m, 24H,
CH(CH3)2), 2.42 (m, 4H, CH(CH3)2), 4.55 and 4.70 (br, 4H each,
C5H4), 7.15 (m, 4H, Ph), 7.33–7.42 (m, 16H, Ph); dC (CDCl3)
16.22 (dd, 2J(CP) = 46.6 Hz, 4J(CP) = 1.9 Hz, CH(CH3)2), 25.79
(d, 1J(CP) = 67.6 Hz, CH(CH3)2), 70.22 (dd, 1J(CP) = 104.2 Hz,
8b. Yield: 0.539 g, 85% (Found: C, 47.19; H, 3.41; N, 2.33.
AgC50H44F6O4P4N2S2Sb requires C, 47.34; H, 3.50; N, 2.21%);
conductivity (acetone, 20 ◦C) 113 X−1 cm2 mol−1; mmax/cm−1 (KBr)
497w, 521m, 591w, 656s (SbF6−), 690s, 742m, 772s, 812w, 902m,
928s, 1023w, 1117m, 1160s, 1191vs, 1267m, 1296m, 1438w, 1486s,
1588m, 2905w, 2960w, 3059w; dH (CD2Cl2) 2.47 (br, 4H, PCH2),
7.06–7.82 (m, 40H, Ph); dC (CD2Cl2) 19.35 (m, PCH2), 121.63
3
1
(d, J(CP) = 4.8 Hz, o-OPh), 125.14 (dd, J(CP) = 104.7 Hz,
3
3
3J(CP) = 5.2 Hz, C of C5H4), 73.64 (d, J(CP) = 11.1 Hz, CH
3J(CP) = 5.4 Hz, i-Ph), 126.50 (s, p-OPh), 129.82 (d, J(CP) =
2
of C5H4), 74.06 (d, J(CP) = 9.5 Hz, CH of C5H4), 121.36 (d,
13.0 Hz, m-Ph), 130.41 (s, m-OPh), 131.86 (d, 2J(CP) = 10.9 Hz,
3J(CP) = 5.2 Hz, o-OPh), 124.08 (s, p-OPh), 129.25 (s, m-OPh),
o-Ph), 134.55 (s, p-Ph), 150.72 (d, J(CP) = 9.6 Hz, i-OPh); MS
2
152.53 (d, 2J(CP) = 9.3 Hz, i-OPh).
(FAB) m/z 1033.8 (100%) [M+ + 1].
2
ꢀ
=
=
=
=
[Ag{j (S,S )-(CH2)n[P{ NP( S)(OR)2}Ph2]2}][SbF6] (n = 1,
R = Et 7a, Ph 7b; n = 2, R = Et 8a, Ph 8b). A solution of the
corresponding bis(iminophosphorane) ligand 1–2a,b (0.5 mmol)
in 30 cm3 of dichloromethane was treated, at room temperature
and in the absence of light, with AgSbF6 (0.172 g, 0.5 mmol) for
1 h. The solvent was then removed under reduced pressure to give
a white solid which was washed with diethyl ether (3 × 20 cm3)
and dried in vacuo.
[Ag{(CH2)n[P{ NP( S)(OR)2}Ph2]2}]x[SbF6]x (n = 4, R =
Et 9a, Ph 9b; n = 6, R = Et 10a, Ph 10b). The polymeric
compounds 9–10a,b, isolated as air-stable white solids, were
prepared as described for 7–8a,b starting from the corresponding
bis(iminophosphorane) ligand 3–4a,b (0.5 mmol) and AgSbF6
(0.172 g, 0.5 mmol).
9a. Yield: 0.442 g, 80% (Found: C, 39.22; H, 4.25; N, 2.60.
AgC36H48F6O4P4N2S2Sb requires C, 39.15; H, 4.38; N, 2.54%);
conductivity (acetone, 20 ◦C) 115 X−1 cm2 mol−1; mmax/cm−1 (KBr)
513w, 542m, 576w, 660s (SbF6−), 694m, 722s, 750m, 791w, 827m,
962s, 1024vs, 1118s, 1161w, 1182m, 1264vs, 1366w, 1390w, 1438s,
1485m, 1590w, 2902w, 2941w, 2986m, 3058w; dH (CDCl3) 1.19 (t,
7a. Yield: 0.430 g, 81% (Found: C, 37.19; H, 3.87; N, 2.66.
AgC33H42F6O4P4N2S2Sb requires C, 37.31; H, 3.98; N, 2.64%);
◦
conductivity (acetone, 20 C) 128 X−1 cm2 mol−1; mmax/cm−1
(KBr) 495m, 541w, 590m, 658vs (SbF6−), 690s, 721m, 744s, 847w,
This journal is
The Royal Society of Chemistry 2007
Dalton Trans., 2007, 2760–2769 | 2765
©