CH), 129.3 (s, CH), 130.3 (s, CH), 131.6 (d, J(13C–31P) = 3.8 Hz),
134.9 (d, J(13C–31P) = 3.0 Hz), 137.6 (d, J(13C–31P) =◦ 5.1 Hz), 137.8
(d, J(13C–31P) = 4.1 Hz), 139.0 (s). IR (ATR, 25 C, cm-1): 3327
(w), 2969 (w), 2943 (w), 2914 (w), 2853 (w), 1610 (w), 1573 (w),
1486 (w), 1421 (s), 1375 (m), 1358 (m), 1260 (m), 1217 (m), 1100
(w), 1070 (w), 1008 (w), 917 (m), 852 (s), 819 (w), 797 (m), 774
(m), 754 (s), 716 (w), 644 (m), 595 (w), 557 (m). Raman (75 mW,
25 ◦C, 3000 scans, cm-1): = 3054 (4), 3017 (5), 2916 (10), 2858 (3),
2730 (1), 1613 (8), 1538 (4), 1482 (2), 1441 (3), 1380 (4), 1306 (10),
1218 (2), 1183 (2), 1166 (1), 1072 (2), 1010 (2), 947 (1), 735 (1),
645 (1), 578 (7), 558 (3), 521 (4), 480 (3), 440 (4), 403 (4), 332 (3),
264 (4), 234 (3), 151 (4). MS (EI, m/z, >10%): 49 (12), 57 (13)
[C4H9]+, 69 (11), 84 (13), 313 (14) [Ter - H]+, 314 (16) [TerNH -
Me]+, 328 (100) [TerNH]+, 358 (23) [M - 2Cl]+, 394 (7) [M - Cl]+,
429 (36) [M]+.
(13) [Ter2N2P]+, 716 (14) [M - 2Cl]+, 735 (18) [M - Me - H]+, 751
(27) [M - Cl]+, 786 (32) [M]+.
Synthesis of [2,6-bis-(2,4,6-trimethylphenyl)phenyl]amino–
diisopropylamino(chloro)arsane (5). To a stirred solution of
N-[2,4-bis-(2,4,6-trimethylphenyl)phenyl]amino(dichloro)arsane
(1.206 g, 2.54 mmol) in diethyl ether (15 mL), a solution of
lithium diisopropylamide LDA (2.55 mmol, freshly prepared
from diisopropylamine (0.258 g, 2.55 mmol) and n-BuLi (2.5M,
2.55 mmol, 1.02 mL) in diethyl ether (15 mL) at -20 ◦C) is added
dropwise at -50 ◦C over a period of 30 min. The resulting yellow
suspension was warmed to ambient temperature and stirred for
three hours. Removal of solvent and drying in vacuo results in a
colourless residue, which was extracted with n-hexane (25 mL)
and filtered (F4), resulting in a colourless solution. Concentration
in vacuo and storage at -25 ◦C resulted in the deposition of
colourless crystals. Removal of supernatant by decantation
and drying in vacuo yields 1.181 g (2.19 mmol, 83%) of 5 as a
Synthesis of 1,3-dichloro-2,4-bis[2,4-bis-(2,4,6-trimethylphenyl)-
phenyl]- cyclo-1,3-diphospha-2,4-diazane (4). To a stirred so-
lution of N-dichlorophosphane-2,6-bis-(2,4,6-trimethylphenyl)-
aniline Ter–NHPCl2 (2.152 g, 5.0 mmol) in n-hexane (50 mL),
a solution of triethylamine Et3N (0.759 g, 7.5 mmol) in n-hexane
◦
colourless crystalline solid. Mp 128 C. Anal. calc.% (found): C,
66.85 (66.71); H, 7.48 (7.48); N, 5.20 (4.67). H NMR (25 ◦C,
1
CD2Cl2, 250.13 MHz): d = 0.76 (d, 6H, CH3, 3J(1H–1H) = 6.7 Hz),
0.97 (d, 6H, CH3, 3J(1H–1H) = 6.7 Hz), 2.08 (s, 6H, CH3), 2.11 (s,
3
6H, CH3), 2.31 (s, 6H, CH3), 3.14 (sept, 2H, CH, J(1H–1H) =
◦
(10 mL) was added dropwise at -80 C, resulting in a colourless
6.7 Hz), 5.05 (s, 1H, NH), 6.94–7.03 (m, 7H, m/p-CH-Ph,
suspension, which was slowly warmed to ambient temperature
over a period of two hours. Stirring for one day at ambient
temperature results in a pale yellowish suspension. The solvent
is removed in vacuo, and the yellowish residue is extracted with n-
hexane (50 mL) and filtered (F4). Removal of solvent and drying
in vacuo results in a pale yellowish solid. Recrystallisation from a
minimum of dichloromethane at 5 ◦C results in the deposition of
colourless crystals. Removal of solvent by decantation and drying
in vacuo yields 1.640 g (2.081 mmol, 83%) of 4 as a colourless,
crystalline solid. Smp. 285 ◦C. Anal. calc.% (found): C, 73.18
(73.20); H, 6.40 (6.84); N, 3.56◦(3.50). (NMR: cis/trans mixture,
m-CH-Mes). 13C { H} NMR (25 ◦C, CD2Cl2, 75.5 MHz): d =
1
20.6 (s, CH3), 21.0 (s, CH3), 21.4 (s, CH3), 24.2 (s, CH(CH3)2),
25.8 (s, CH(CH3)2), 48.2(s, CH(CH3)2), 121.2 (s, aryl-CH), 129.3
(s, aryl-CH), 129.4 (s, aryl-CH), 129.8 (s, aryl-CH), 130.3, 135.7,
137.9, 138.2, 138.4, 140.8. IR (ATR, 32 scans): 3338 (w), 3303
(w), 2960 (s), 2916 (m), 2860 (w), 2726 (w), 1611 (w), 1585 (w),
1485 (w), 1454 (m), 1434 (m), 1418 (s), 1378 (m), 1365 (m), 1306
(w), 1284 (w), 1258 (m), 1242 (m), 1224 (m), 1191 (m), 1168 (s),
1152 (s), 1118 (s), 1096 (m), 1074 (m), 1032 (w), 1014 (m), 944
(s), 884 (w), 848 (s), 814 (m), 805 (m), 791 (m), 759 (s), 744 (m),
718 (m),◦647 (m), 604 (w), 577 (w), 565 (m), 550 (m). Raman (200
mW, 25 C, 251 scans, cm-1): = 3341 (1), 3051 (4), 3015 (4), 2961
(6), 2920 (10), 2864 (4), 2755 (2), 2735 (2), 1612 (3), 1586 (2), 1484
(1), 1441 (2), 1422 (1), 1380 (2), 1305 (4), 1285 (2), 1245 (1), 1261
(1), 1225 (3), 1182 (1), 1076 (1), 1007 (1), 946 (1), 850 (1), 642 (1),
743 (1), 722 (1), 644 (1), 603 (1), 578 (1), 550 (1), 520 (1), 465 (1),
447 (2), 407 (1), 359 (1), 336 (1), 306 (1), 281 (1), 248 (1), 230 (1),
177 (1), 130 (1). MS (CI, isobutane, m/z): 102 [N(iPr)2]+, 330 [Ter
- NH3]+, 402 [Ter - NAs]+, 438 [M - N(iPr)2]+, 503 [M - Cl]+, 538
[M]+.
1
approx. 1 : 3) 31P{ H} NMR(25 C, CD2Cl2, 121.5MHz): d = 227.4
◦
1
(s, cis), 264.1 (s, trans). H NMR (25 C, CD2Cl2, 300.13 MHz):
d = 1.84 (d, 12H, 7J(31P–1H) = 1.7 Hz, trans, o-CH3), 1.90 (s, 12H,
cis, o-CH3), 2.35 (s, 6H, cis, p-CH3), 2.46 (s, 6H, trans, p-CH3),
6.72–6.86 (m, 6H, cis/trans), 7.01 (m, 1H, 3J(1H–1H) = 7.6 Hz, cis,
3
1
p-CH), 7.06 (t, 1H, J(1H–1H) = 7.6 Hz, trans, p-CH). 13C{ H}
NMR (25 ◦C, CD2Cl2, 75.5 MHz): d = 21.0 (s, o-CH3), 21.3 (t,
J(13C–31P) = 2.7 Hz, o-CH3), 21.8 (s, p-CH3), 21.9 (t, J(13C–31P) =
3.7 Hz, p-CH3), 123.7 (s, CH), 124.8 (s, CH), 128.8 (s, CH), 129.1
(s, CH), 131.3 (s, CH), 131.6 (s, CH), 132.4 (t, J(13C–31P) = 1.9 Hz),
134.4 (s), 134.6 (s), 135.2 (t, J(13C–31P) = 2.8 Hz), 135.7 (t, J(13C–
31P) = 2.9 Hz), 136.1 (t, J(13C–31P) = 2.8 Hz), 137.9 (s), 138.3 (t,
J(13C–31P) = 4.4 Hz), 138.8 (t, J(13C–3◦1P) = 3.5 Hz), 138.9 (t, J(13C–
31P) = 3.5 Hz). Raman (150 mW, 25 C, 8 scans, cm-1): = 3047 (2),
3013 (2), 2918 (10), 2855 (2), 2732 (1), 1612 (4), 1583 (3), 1485 (1),
1431 (2), 1378 (2), 1305 (5), 1287 (2), 1166 (1), 1094 (1), 1007 (1),
942 (1), 740 (1), 577 (4), 562 (2), 540 (3), 524 (2), 483 (1◦), 438 (2),
387 (1), 338 (1), 264 (1), 227 (2), 203 (2). IR (ATR, 25 C, cm-1):
2972 (w), 2943 (w), 2914 (w), 2852 (w), 1610 (m), 1573 (w), 1417
(s), 1373 (m), 1357 (m), 1262 (w), 1219 (m), 1070 (w), 1032 (w),
1007 (w), 911 (m), 889 (m), 850 (w), 796 (m), 753 (m), 740 (w), 700
(w), 643 (w), 558 (w), 550 (w). MS (EI, m/z, >10%): 36 (17), 41
(13) [C3H5]+, 44 (33), 57 (17) [C4H9]+, 69 (11), 296 (12) [Ter - Me
- 2H]+, 310 (40) [Ter - 3H]+, 326 (50) [Ter - N - H]+, 342 (64) [Ter
- NP - Me]+, 358 (100) [Ter - NP]+, 393 (25) [Ter - NPCl]+, 671
Synthesis of 2-[2,6-bis-(2,4,6-trimethylphenyl)phenyl]amino-2-
arsa-3,7-diaza-tricyclo[5.4.1.03,12]dodec-3(12)-enylium chloride (6).
To
a stirred solution of N-[2,4-bis-(2,4,6-trimethylphenyl)-
phenyl]amino(dichloro)-arsane (0.949 g, 2.0 mmol) in diethyl ether
(20 mL), a solution of DBU (0.335 g, 2.2 mmol) in diethyl
ether (10 mL) is added dropwise at -10 ◦C over a period of
10 min. The resulting yellow suspension is warmed to ambient
temperature and is stirred for ten hours. The resulting colourless
suspension is filtered (F4) and the solvent is removed in vacuo,
resulting in a colourless froth. Recrystallistation from diethyl ether
(10 mL) at -25 ◦C gave a mixture of several compounds from
which 2-[2,6-bis-(2,4,6-trimethylphenyl)phenyl]amino-2-arsa-3,7-
diaza-tricyclo[5.4.1.03,12]dodec-3(12)-enylium chloride 6 could be
identified by an X-ray crystallographic analysis. A preparative
separation was not successful.
9970 | Dalton Trans., 2010, 39, 9962–9972
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The Royal Society of Chemistry 2010
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