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of paper B30303715k
N9-(2'-chloroethyl)adenine (1).18,19 To adenine (27 g, 200 mmol) and sodium hydride
(60% dispersion in oil, 10 g, 250 mmol) in anhydrous DMF (500 ml) was added 1bromo-2-chloroethane. The mixture was stirred under an atmosphere of nitrogen for 48 h.
The resulting suspension was filtered through celite. The solvent was removed from the
filtrate by rotary evaporation and the crude product was recrystallised from ethanol (180
ml). This yielded the product as a white powder (16.3 g, 41%). Microanalysis (%): Found
(Calc. for C7H8N5Cl). C, 42.14 (42.54); H, 3.49 (4.08); N, 35.58 (35.44). IR (KBr disc,
cm-1): 3351m, 3328m, 3233m, 1654vs, 1598vs, 1579s, 1514w, 1483s, 1436m, 1420m,
1366m, 1325s, 1302s, 1243s, 1217w, 1138w, 1069m, 1033w, 1003w, 954m, 901m,
851w, 795m, 752w, 732w, 718m, 687w, 657m, 645w, 606m, 593w, 537m, 458m, 352w,
317w. CIMS (m/z): 198 [M + H]+, 164 [M -HCl]+. EIMS: 197 [M]+, 162 [M-Cl]+, 135
[M-CH2CH2Cl]+.
N9-(2'-azidoethyl)adenine (2).20 (3.204 g, 16.20 mmol) and sodium azide (3.145 g, 48.5
mmol) was mixed in DMSO ( 15 cm3). The mixture was stirred at 80C for 24 hr. The
solvent was removed under rotary evaporation. To the residue was added water (30 cm3).
The solid was filtered off and washed with water (3  10 cm3) and ethanol (2  10 cm3)
and ethyl ether (3  10 cm3) to give 1.70 g of the product. The aqueous and the organic
washing filtrates were combined and extracted with dichloromethane (3  100 cm3) to
gave another crop of product (0.63 g). Total yield: 2.33 g, 71.0%. Microanalysis (%):
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Found (Calc. for C7H8N8). C, 41.53 (41.17); H, 3.49 (3.49); N, 55.59 (54.88). IR (KBr
disc, cm-1): 3270w, 3106m, 2100vs, 1677s, 1604vs, 1574m, 1479m, 1421m, 1363w,
1317w, 1305m, 1300m, 1273m, 1238m, 1206w, 1170w, 1082w, 1061m, 1017m, 921w,
905w, 846w, 774m, 720w, 666m, 608m, 541w. CIMS (m/z): 205 [M + H] +. EIMS: 204
[M]+, 176 [M-N2]+, 148 [M-CH2N3]+.
N9-(2'-aminoethyl)adenine (3).21 9-(2-azidoethyl)adenine (0.48 g, 2.36 mmol) was
dissolved in ethanol (120 cm3). To this solution was added palladium on carbon (10%,
0.230 g) and hydrogen gas was bubbled in. The reaction ended in about 6 hr. according to
TLC analysis. The resulting solution was heated to reflux and filtered through celite
while hot to remove the catalyst. Solvent removal of the filtrate by rotary evaporation
gave the product as a white solid. Yield: 0.406 g, 96.4 %. Microanalysis (%): Found
(Calc. for C7H10N6). C, 47.99 (47.18); H, 4.45 (5.66); N, 45.77 (47.16). IR (KBr disc, cm1
): 3349m, 3194m, 3091w, 2786w, 1656vs, 1596vs, 1506s, 1437w, 1422m, 1380m,
1367vw, 1341m, 1322m, 1308m, 1277vw, 1252m, 1229w, 1149w, 1128w, 1050w,
1004w, 982w, 896m, 861m, 796m, 766m, 735w, 711w, 646m, 609w, 582m, 536m. CIMS
(m/z): 179 [M + H]+. EIMS: 178 [M]+, 163 [M-NH2]+, 148 [M-CH2NH2]+.
N9-(N2'-n-propylaminoethyl)adenine (4). (4.0 g, 20 mmol) and neat n-propylamine (50
cm3, 600 mmol) was stirred at room temperature under a nitrogen atmosphere for 4 days.
The excess n-propylamine was removed under vacuum and the residue was recrystallized
from ethanol to give the product as a white solid. Yield: 3.0 g, 68.10%.
Microanalysis(%): Found (Calc. for C10H16N6). C, 54.53 (54.60); H, 7.32 (7.00); N, 38.15
(38.54). IR (KBr disc, cm-1): 3343w, 3311w, 3251m, 3140br s, 2966w, 2948w, 2886w,
2870w, 2815m, 1665vs, 1598vs, 1578m, 1481s, 1431w, 1413m, 1397w, 1389w, 1367m,
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1350w, 1324s, 1310s, 1270w, 1254m, 1232w, 1207w, 1139w, 1114m, 1084w, 1064w,
1051m, 1017m, 963w, 938w, 897w, 886m, 872w, 836m, 797m, 764w, 718m, 648w,
609w, 588m, 559w, 534w. CIMS (m/z): 221 [M + H]+.
N9-(N2'-diphenylphosphinoylaminoethyl)adenine (5) To a solution of L1 (200 mg, 0.55
mmol) in THF (200 cm3) was added aqueous hydrogen peroxide (65 l, 0.57 mmol). The
mixture was stirred at 0C for 1 hr and then dried over magnesium sulfate and filtered.
The filtrate was concentrated to ca. 1 cm3. The solid precipitated was collected by suction
filtration washed with THF (2  1 cm3) and Et2O (2  1 cm3). Yield: 154 mg, 74%.
Microanalysis (%): Found (Calc. for C19H19N6PO). C, 57.45 (60.31); H, 5.25 (5.06); N,
20.10 (22.20). IR (KBr disc, cm-1): 3433s, 3343m, 3265m, 3194m, 2980w, 2941w,
2869w, 1627vs, 1600vs, 1466sm, 1439m, 1416m, 1361w, 1326m, 1305m, 1242m, 1180s,
1165s, 1124s, 1057w, 998w, 933w, 798w, 753w, 726m, 698m, 559s, 527m. EIMS (m/z):
378 [M]+, 243 [M-Ade]+, 230 [M-AdeCH2]+.
N9-(N2'-diphenylthiophosphinoylaminoethyl)adenine (7). To a solution of L1 (102 mg,
281umol) in THF (50 cm3) was added elemental sulfur (100 mg, 1.06 mmol). The
mixture was refluxed for 2 hr and then concentrated to ca. 1 cm3. Addition of Et2O (10
cm3), filtration and washing with Et2O (3  1 cm3) gave the product as a white solid.
Yield: 98 mg, 88%. Microanalysis (%): Found (Calc. for C19H19N6PS). C, 56.85 (57.86);
H, 4.75 (4.86); N, 21.09 (21.31). IR (KBr disc, cm-1): 3313m, 3144m, 2963w, 1654s,
1598vs, 1575m, 1475m, 1437s, 1416m, 1385w, 1358vw, 1358w, 1322w, 1305m, 1261s,
1238m, 1205w, 1165w, 1111s, 1051w, 1023m, 997vw, 944w, 927w, 914vw, 897vw,
797s, 750w, 718s, 693m, 645m, 627m, 614m, 593w, 534vw, 516w, 503w. EIMS (m/z):
394 [M]+, 262 [M-S]+, 259 [M-Ade]+.
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N9-(N2'-diphenylselenophosphinoylaminoethyl)adenine (9). To a solution of L1 (77
mg, 0.199 mmol) in THF (50cm3) was added excess elemental selenium (18 mg, 0.228
mmol). The mixture was refluxed overnight and then cooled to room temperature. The
excess selenium was filtered off through a celite pad. The filtrate was vacuumed to
dryness and the sticky residue was taken up by Et2O (5 cm3). The clear white solid was
collected by suction filtration and washed with Et2O (3  1 cm3). Yield: 75 mg, 86%.
Microanalysis(%): Found (Calc. for C19H19N6PSe). C, 51.93 (51.71); H, 4.10 (4.34); N,
18.34 (19.04). IR (KBr disc, cm-1): 3308m, 3146m, 2959w, 2925w, 2869w, 1664vs,
1600vs, 1578m, 1478m, 1453vw, 1436s, 1417s, 1379w, 1363w, 1322m, 1309m, 1246m,
1209w, 1174w, 1126m, 1098s, 1070m, 1016w, 982m, 893vw, 797m, 761w, 747w, 728w,
712w, 696s, 650m, 617vw, 586m, 570m, 557m, 526w, 508m, 495w, 414w. EIMS (m/z):
442 [M]+, 361 [M-Se]+, 307 [M-Ade]+.
N9-(N2'-diphenylphosphino-N2'-n-propylaminoethyl)adenine (L2). To a solution of 4
(2.277 g, 8.87 mmol) and triethylamine (3.0 cm3, 21 mmol) in dichloromethane was
added dropwise a solution of Ph2PCl (1.6 cm3, 8.91 mmol) in dichloromethane in 30 min
at room temperature. The mixture was stirred for another 2 hr. The solvent was replaced
by THF (200 cm3). The salt was filtered off and washed with THF (2  20 cm3) through
sinter frit under a nitrogen atmosphere. The filtrate was concentrated to ca. 20 cm3 and
Et2O (30 cm3) was added to precipitate the product. Yield: 2.926 g, 61%. Microanalysis
(%): Found (Calc. for C22H25N6P). C, 64.43 (65.33); H, 6.41 (6.23); N, 20.89 (20.78). IR
(KBr disc, cm-1): 3311m, 3124br s, 2959m, 2930w, 2869w, 1665vs, 1598vs, 1574m,
1481m, 1417m, 1432s, 1386w, 1360w, 1329m, 1307s, 1250s, 1209w, 1185m, 1123m,
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1090w, 1069m, 1018m, 987s, 798m, 742m, 756m, 698s, 662m, 607w, 536m, 498w,
447w, 342w, 279m, 252m. CIMS (m/z): 405 [M + H], 221 [M - PPh2]+.
N9-( N2'-diphenylphosphinoyl-N2'-n-propylaminoethyl)adenine (6). To a solution of
L2 (150 mg, 0.371 mmol) in THF (50 cm3) was added aqueous hydrogen peroxide (45 l,
0.40 mmol). The mixture was stirred at 0C for 20 min and at room temperature for 1 h.
After drying over magnesium sulfate and filtration, the filtrate was vacuumed to dryness
and the residue was washed with Et2O (3  3 cm3) to give the product as a white solid.
Yield: 140 mg, 90%. Microanalysis (%): Found (Calc. for C22H25N6PO). C, 59.80
(62.58); H, 6.48 (5.99); N, 18.74 (19.99). IR (KBr disc, cm-1): 3470m, 3382m, 3268m,
3114m, 2961w, 2934w, 2874w, 1677vs, 1645m, 1606vs, 1578s, 1518w, 1477s, 1440s,
1418s, 1389w, 1378w, 1368w, 1360m, 1333m, 1306s, 1288w, 1259w, 1248m, 1200m,
1183s, 1170s, 1123s, 1103m, 1068m, 1014w, 987s, 956w, 937w, 922m, 899w, 876m,
799m, 758w, 741w, 727m, 713m, 696m, 645w, 568w, 549m, 526w, 447w. EIMS (m/z):
421 [M]+, 391 [M - C2H3]+, 285 [M-Ph]+.
N9-(N2'-diphenylthiophosphinoyl-N2'-n-propylaminoethyl)adenine (8). To a solution
of L2 (203 mg, 0.5 mmol) in THF (50 cm3) was added elemental sulfur (18 mg, 0.56
mmol). The mixture was refluxed under a nitrogen atmosphere for 2 hr and then cooled to
room temperature and passed though a short celite pad. The filtrate was vacuumed to
dryness to give the product as a white solid. Yield: 200 mg, 92%. Microanalysis (%):
Found (Calc. for C22H25N6PS). C, 59.63 (60.53); H, 5.92 (5.77); N, 18.67 (19.25). IR
(KBr disc, cm-1): 3325m, 3153m, 2960m, 2928w, 2868w, 1656vs, 1596vs, 1514vw,
1479s, 1435s, 1418s, 1386w, 1361w, 1325m, 1308m, 1262s, 1250m, 1212w, 1177m,
1156w, 1104s, 1066v, 1017s, 998w, 982m, 899w, 876vw, 862vw, 852vw, 797s, 765m,
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725s, 719s, 691m, 651w, 637m, 631m, 615w, 606w, 581w, 538w, 523m, 507m, 472w,
450w. EIMS (m/z): 437 [M]+, 405 [M - S]+, 301[M-Ade]+.
N9-(N2'-diphenylselenophosphinoyl- N2'-n-propylaminoethyl)adenine (10).
To a
solution of L2 (151 mg, 0.375 mmol) in THF (50 cm3) was added elemental selenium (50
mg, 0.633 mmol). The mixture was refluxed under a nitrogen atmosphere overnight and
then cooled to room temperature and filtered though a short celite pad. The filtrate was
vacuumed to dryness and the residue was washed with Et2O (3  3 cm3) to give the
product as a white solid. Yield: 160 mg, 88%. Microanalysis (%): Found (Calc. for
C22H25N6PSe). C, 54.38 (54.66); H, 4.94 (5.21); N, 17.74 (17.38). IR (KBr disc, cm-1):
3298 br m, 3128 br m, 2912w, 2861w, 1659s, 1597vs, 1575m, 1511vw, 1476s, 1436s,
1416s, 1387w, 1358w, 1323m, 1305m, 1256w, 1239m, 1204m, 1165m, 1107s, 1059w,
1024w, 998w, 845vw, 796s, 744s, 714m, 705m, 692s, 649w, 619w, 597w, 578m, 559s,
549m, 537w, 493m, 414w. EIMS (m/z): 484 [M]+, 403 [M - Se]+, 348 [M-Ade]+, 265
[Ph2PSe]+, 219 [M-Ph2PSe]+.
[RhCl(cod)(L1)] (13) To a solution of [Rh(-Cl)(cod)]2 (70 mg, 142 mol) in THF (20
cm3) was added L1 (103 mg, 284 mol). The reaction mixture was stirred for 20 min and
concentrated in vacuum to ca. 0.5 cm3. Addition of Et2O and filtration washing with Et2O
(3  1 cm3) give the product as a yellow solid. Yield: 139 mg, 80%. Microanalysis (%):
Found (Calc. for C29H34Cl2N6PRh). C, 53.63 (53.26); H, 5.71 (5.13); N, 12.44 (13.80). IR
(KBr disc, cm-1): 3383m, 3321m, 3154m, 3055w, 2938w, 2917w, 2878m, 2832m,
1638vs, 1569s, 1512w, 1477s, 1434s, 1416m, 1361w, 1328m, 1304m, 1254w, 1240m,
1203w, 1183w, 1168w, 1098s, 1056w, 1027w, 997w, 963w, 919w, 865w, 798w, 749m,
697s, 649m, 549m, 505w, 483vw, 467vw, 282w.
FABMS+ (m/z): 573 [M - Cl]+.
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[RhCl2(5-C5Me5)(L1)] (15) To a suspension of [RhCl(-Cl)(5-C5Me5)]2 (100 mg, 161
mol) in THF (40 cm3) was added L1 (117 mg, 323 mol). The suspension of [RhCl(Cl)(5-C5Me5)]2 and L1 disappeared gradually and the solution developed into deep red
solution. Stirring was continued for 1 h. Concentration to ca. 1 cm3 in vacuum and
addition of Et2O (20 cm3) led to the precipitation of the orange product yield: 203 mg,
94%. Microanalysis (%): Found (Calc. for C29H34Cl2N6PRh). C, 51.48 (51.88); H, 4.87
(5.10); N, 12.00 (12.52). IR (KBr disc, cm-1): 3412s, 3374m, 3336m, 3193w, 3051w,
2981w, 2916w, 2869w, 1626vs, 1594s, 1507w, 1473m, 1437m, 1414m, 1373w, 1354w,
1327m, 1301m, 1246m, 1201w, 1184w, 1167m, 1100s, 1074w, 1054w, 1023m, 798m,
749s, 698s, 651m, 549s, 507w, 472m. FABMS+ (m/z): 671 [M + H]+, 693 [M + Na]+,
653 [M - Cl]+, 599[M - 2Cl]+.
[IrCl2(5-C5Me5)(L1)] (17) To a solution of L1 (91 mg, 251 mol) in THF (40 cm3) was
added [IrCl(-Cl)(5-C5Me5)]2 (100 mg, 126 mol). The reaction mixture was stirred for
1 hr. The solvent was removed in vacuo. The residue was washed with Et2O (3  1 cm3)
to give the product as an orange powder. Yield: 170 mg, 89%. Microanalysis (%): Found
(Calc. for C29H34Cl2N6PIr). C, 46.27 (45.79); H, 5.18 (4.05); N, 10.36 (11.05). IR (KBr
disc, cm-1): 3419m, 3329m, 3249w, 3184w, 3312w, 3055w, 2981w, 2918w, 2851w,
1643vs, 1597s, 1575w, 1511w, 1475m, 1437m, 1413s, 1379w, 1359w, 1329m, 1296m,
1240m, 11204w, 1182w, 1163m, 1115m, 1103s, 1070w, 1054m, 1029m, 998w, 923m,
896w, 859w, 798m, 756s, 708s, 699s, 651s, 618w, 610w, 570w, 555s, 539w, 507w,
485m, 450w. FABMS+ (m/z): 761 [M + H]+, 783 [M + Na]+.
[RuCl2(3, 3-C10H16)(L1)] (19) To a solution of [Ru(-Cl)Cl(3, 3-C10H16)]2 (50 mg,
81 mol) in THF (10 cm3) was added L1 (59 mg, 163 mol). The reaction mixture was
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stirred for 20 min and vacuumed to dryness. The residue was washed with Et2O (3  1
cm3) to give the product as a pale brown solid. Yield: 96 mg, 84%. Microanalysis (%):
Found (Calc. for C29H35Cl2N6PRu). C, 51.75 (51.94); H, 5.18 (5.26); N, 12.56 (12.53). IR
(KBr disc, cm-1): 3450m, 3296m, 3249m, 3154w, 3134w, 3051w, 2956w, 2918w, 2858w,
1641vs, 1595s, 1480m, 1436m, 1413m, 1383m, 1359w, 1345w, 1324w, 1300m, 1252m,
1238m, 1197w, 1164w, 1101w,, 1089s, 1052w, 1023w, 996w, 923w, 893vw, 860w,
816w, 798m, 748m, 698s, 649w, 598w, 570w, 543s, 495vw, 474m, 413w, 306w.
FABMS+ (m/z): 671 [M + H]+, 693 [M + Na]+.
[RuCl2(6-p-MeC6H4iPr)(L1)] (20). To a solution of [RuCl(-Cl)(6-p-MeC6H4iPr]2
(80mg, 131 mol) in THF (20 cm3) was added L1 (95 mg, 262 mol). Red solid of the
product precipitated out in about 10 min. The stirring was continued for 1 h. The product
was filtered off and washed with Et2O (3  1 cm3) and dried in vacuum. Yield: 152 mg,
87.0%. Microanalysis (%): Found (Calc. for C29H33Cl2N6PRu). C, 51.10 (52.10); H, 5.20
(4.98); N, 12.08 (12.57). IR (KBr disc, cm-1): 3426m, 3358m, 3315w, 3172m, 3111vw,
3079vw, 3032w, 2960w, 2868w, 1655vs, 1560s, 1577m, 1515vw, 1498vw, 1480m,
1434m, 1406m, 1387vw, 1358w, 1330w, 1297m, 1258w, 1243w, 1202w, 1184w, 1163w,
1101s, 1055m, 1028vw, 998vw, 942vw, 920w, 905w, 872w, 858w, 797w, 749m, 700s,
649s, 589vw, 572vw, 551m, 535w, 503w, 485m.
FAB+ (m/z): 669 [M + H]+, 693 [M +
Na]+.
[PtMe2(L1)2] (21). [PtMe2(cod)]2 (40 mg, 120 mol) and L1 (87 mg, 240 mol) were
mixed in CH2Cl2 (40 cm3).
The reaction mixture was stirred for 1 hr and then
concentrated to ca 0.5 cm3. Et2O (5 cm3) was added to precipitate the product. Filtration
and washing with light petroleum ether (3  1 cm3) and Et2O (3  1 cm3) gave the product
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as a white solid. Yield: 106 mg, 93%. Microanalysis (%): Found (Calc. for
C40H44N12P2Pt). C, 49.71 (50.58); H, 4.58 (4.67); N, 17.05 (17.70). IR (KBr disc, cm-1):
3322m, 3174m, 3050w, 2930m, 2872m, 1642vs, 1596s, 1509vw, 1478s, 1435m, 1417m,
1301m, 1240m, 12031w, 1181w, 1162w, 1100s, 1055w, 1027vw, 996w, 920m, 846vw,
798m, 747m, 698vs, 649m, 559vw, 541m, 508vw, 472vw.
FABMS+ (m/z): 949 [M ]+,
934 [M - CH3]+, 919 [M - 2CH3]+.
[Au(Cl)(L2)] (12). To L2 (68 mg, 168 mol) in dichloromethane (30 cm3) was added
[AuCl(tht)] (54 mg, 168 umol). The mixture was stirred at room temperature for 30 min
and then vacuumed to ca. 0.5 cm3. Et2O was added and the solid was filtered off and
washed with Et2O (3  3 cm3). Yield: 105 mg, 98%. Microanalysis (%): Found (Calc. for
C22H26AuClN6P). C, 42.09 (41.43); H, 4.27 (4.11); N, 12.42 (13.18). IR (KBr disc, cm-1):
3424m, 3320m, 3152m, 2961m, 2923w, 2862w, 1665s, 1641vs, 1599vs, 1576m, 1507vw,
1475s, 1436s, 1416m, 1364w, 1322m, 1305m, 1247m, 1213w, 1171m, 1104s, 1063w,
991w, 798w, 750w, 732w, 695s, 650m, 559m, 518w, 477w, 331w. FAB (m/z): 638 [M +
H]+, [M - Cl]+.
[RhCl(cod)(L2)] (14) To a solution of [Rh(-Cl)(cod)]2 (99 mg, 201 mol) in CH2Cl2
(20 cm3) was added L2 (164 mg, 404 mol). The reaction mixture was stirred for 20 min
and vacuumed to dryness. The residue was washed with Et2O (3  1 cm3) gave the
product as an orange solid. Yield: 243 mg, 92 %. Microanalysis (%): Found (Calc. for
C30H37ClN6PRh). C, 53.85 (55.37); H, 5.49 (5.74); N, 12.68 (12.92). IR (KBr disc, cm-1):
3391m, 3321m, 3172m, 3073w, 3053w, 2959m, 2933m, 2873m, 2831w, 1638vs, 1595vs,
1509vw, 1475s, 1433s, 1416m, 1383vw, 1356w, 1328m, 1299m, 1245m, 1207w, 1177m,
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1122w, 1094m, 1073w, 1028vw, 987m, 917vw, 890w, 863w, 798m, 748m, 726w, 699s,
649m, 541s, 506w, 482w, 465w.
FABMS+ (m/z): 615 [M - Cl]+.
[RhCl2(C5Me5)(L2)] (16) [RhCl(-Cl)(5-C5Me5)]2 (76 mg, 123 mol) and L2 (100 mg,
247 mol) was mixed in THF (20 cm3). The reaction mixture was stirred for 2hr and
vacuumed to dryness. The solid was washed with Et2O (3  1 cm3) to give the product as
an deep red solid. Yield: 166 mg, 94.86 %. Microanalysis (%): Found (Calc. for
C32H40Cl2N6PRh). C, 54.97 (53.87); H, 4.20 (5.65); N, 10.76 (11.78). IR (KBr disc, cm1
): 3405m, 3324m, 3173m, 3054w, 2963m, 2926w, 2872w, 1637vs, 1595s, 1509w,
1474m, 1436m, 1416m, 1374w, 1357w, 1326m, 1299m, 1245m, 1207w, 1169w, 1120w,
1097m, 1074w, 1022w, 978m, 894w, 864w, 799m, 751m, 723w, 700s, 650m, 610w,
538s, 514w, 481w, 350vw. FABMS+ (m/z): 713 [M]+, 677 [M - Cl]+, 641 [M - 2Cl +
H]+.
[IrCl2(C5Me5)(L2)] (18) [IrCl(-Cl)(5-C5Me5)]2 (78 mg, 98 mol) and L2 (80 mg, 198
mol) was mixed in THF (20 cm3). The reaction mixture was stirred for 2hr and
vacuumed to dryness. The solid was washed with Et2O (3  1 cm3) to give the product as
an orange solid. Yield: 150 mg, 94.9 %. Microanalysis (%): Found (Calc. for
C32H40Cl2N6PIr). C, 48.08 (47.88); H, 5.18 (5.02); N, 10.05 (10.47). IR (KBr disc, cm-1):
3403m, 3312w, 3091w, 3058w, 2965m, 2923w, 2872w, 1660vs, 1634vs, 1600s, 1576m,
1507vw, 1481s, 1434s, 1416m, 1376m, 1326m, 1301m, 1272vw, 1244m, 1207vw,
1194vw, 1162w, 1119w, 1098s, 1075m, 1028m, 976m, 896m, 862w, 799m, 776w, 749m,
726m, 704s, 690m, 648m, 619w, 606w, 543s, 518m, 486m, 463w, 291w.
(m/z): 803 [M + H]+, 767 [M - Cl]+, 731 [M - 2Cl + H]+.
FABMS+
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[PtCl2(L2)2] (22). To a solution of L2 (84 mg, 21 mol) in CH2Cl2 (20 cm3) was added
[PtCl2(cod)] (38 mg, 10 mol). The reaction mixture was stirred for 1 hr and passed
through a short Celite pad. The filtrate was concentrated to ca. 1 cm3. Addition of Et2O
(10 cm3) led to the precipitation of the product. Filtration and washing with light
petroleum (3  1 cm3) and Et2O (3  1 cm3) gave the product as a white solid. Yield: 105
mg, 95.5 %. Microanalysis (%): Found (Calc. for C44H50Cl2N12P2Pt). C, 48.10 (49.20); H,
4.86 (4.69); N, 15.37 (15.66). IR (KBr disc, cm-1): 3330m, 3175m, 3058w, 29632m,
2932w, 2873m, 1638vs, 1596s, 1509vw, 1473s, 1437s, 1416m, 1356w, 1327m, 1299m,
1246m, 1206w, 1168w, 1098s, 1073w, 1030w, 982m, 917vw, 890w, 859w, 798m, 749m,
697s, 649m, 562w, 517s, 306w.
FAB+ (m/z): 1039 [M - Cl]+, 1003 [M - 2Cl]+.
Supplementary Material (ESI) for Dalton Transactions
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Table S1 NMR spectroscopic data for compound 1-4
Entry
1
2
3
1
H NMR
H ( DMSO-d6, ppm)
8.17 (s, 1H, C8-H)
8.16 (s, 1H, C2-H)
7.27 (br s, 2H, NH2)
4.51 (t, 2H, AdeCH2CH2)
4.07 (t, 2H, AdeCH2CH2 )
8.16 (s, 2H, C8-H + C2-H)
7.25 (br s, 2H, NH2)
4.33 (t, 2H, AdeCH2CH2)
3.78 (t, 2H, AdeCH2CH2 )
8.13 (s, 1H, C2-H)
8.10 (s, 1H, C8-H)
7.17 (br s, 2H, NH2)
4.10 (t, 2H, AdeCH2CH2)
2.92 (t, 2H, AdeCH2CH2 )
1.48 (br s, 2H, CH2NH2 )
1
13
H NMR
J (Hz)
3
JCHCH = 6
JCHCH = 6
3
3
JCHCH = 6
JCHCH = 6
3
3
JCHCH = 6
JCHCH = 6
3
H (ppm, CDCl3)
8.25 (s, 1H, C2-H)
7.84 (s, 1H, C8-H)
6.05 (br s, 2H, NH2)
4.48 (t, 2H, AdeCH2CH2)
3.88 (t, 2H, AdeCH2CH2 )
8.38 (s, 1H, C2-H)
7.86 (s, 1H, C8-H)
5.67 (br s, 2H, NH2)
4.36 (t, 2H, AdeCH2CH2)
3.82 (t, 2H, AdeCH2CH2 )
8.25 (s, 1H, C8-H)
7.85 (s, 1H, C2-H)
6.03 (br s, 2H, NH2)
4.18 (t, 2H, AdeCH2CH2 )
3.09 (t, 2H, AdeCH2CH2 )
2.60 (br s, NH2)
J (Hz)
3
JCHCH = 6
JCHCH = 6
3
3
JCHCH = 6
JCHCH = 6
3
3
JCHCH = 6
JCHCH = 6
3
C-{1H} NMR
C (DMSO-d6, ppm)
13
C-{1H} NMR
C (CDCl3 + DMSO-d6 for
1-3, CDCl3 for 4, ppm)
155.98 (C6)
152.51 (C2)
149.55 (C4)
141.08 (C8)
118.68 (C5)
44.73 (AdeCH2CH2)
42.91(AdeCH2CH2)
155.18 (C6)
152.46(C2)
149.18(C4)
140.29 (C8)
119.04 (C5)
44.98 (AdeCH2CH2)
41.84 (AdeCH2CH2)
156.63 (C6)
153.18 (C2)
150.26 (C4)
141.51 (C8)
119.29 (C5)
50.20 (AdeCH2CH2)
42.91(AdeCH2CH2)
155.53 (C6)
153.26 (C2)
150.03 (C4)
140.88 (C8)
119.80 (C5)
50.39 (AdeCH2CH2)
43.25 (AdeCH2CH2)
155.95 (C6)
152.29 (C2)
149.61 (C4)
141.29 (C8)
118.77 (C5)
46.31 (AdeCH2CH2)
41.35 (AdeCH2CH2)
155.13 (C6)
152.29 (C2)
149.49 (C4)
140.37 (C8)
119.06 (C5)
46.40 (AdeCH2CH2)
41.11 (AdeCH2CH2)
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4
8.23 (s, 1H, C2-H)
8.20 (s, 1H, C8-H)
7.27 (br s, 2H, NH2)
4.27 (t, 2H, AdeCH2CH2)
3.38 (br s, NH + H2O in
2.99 (t, 2H, AdeCH2CH2 )
2.55 (t, 2H, NCH2CH2CH3)
1.43 (sxt, 2H, NCH2CH2CH3)
0.90 (t, 3H, NCH2CH2CH3)
3
JCHCH = 6
3
JCHCH = 6
JCHCH = 7
3
JCHCH = 7
3
JCHCH = 7
3
8.37 (s, 1H, C2-H)
7.92 (s, 1H, C8-H)
5.75 (br s, 2H, NH2)
4.30 (t, 2H, AdeCH2CH2)
3.08 (t, 2H, AdeCH2CH2 )
2.60 (t, 2H, NCH2CH2CH3)
1.47 (sxt, 2H,
NCH2CH2CH3)
1.15 (br s, NH)
0.89 (t, 3H, NCH2CH2CH3)
3
JCHCH
JCHCH
3
JCHCH
3
JCHCH
3
3
=6
=6
=7
=7
JCHCH = 7
155.95 (C6)
152.29 (C2)
149.61 (C4)
141.29 (C8)
118.77 (C5)
50.59 (NCH2CH2CH3)
48.29 (AdeCH2CH2)
42.91 (AdeCH2CH2)
22.46 (NCH2CH2CH3)
11.67 (NCH2CH2CH3)
155.65 (C6)
153.14 (C2)
150.39 (C4)
141.42 (C8)
119.91 (C5)
51.64 (NCH2CH2CH3)
49.04 (AdeCH2CH2)
44.35 (AdeCH2CH2)
23.40 (NCH2CH2CH3)
11.88 (NCH2CH2CH3)
Supplementary Material (ESI) for Dalton Transactions
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Table S2 NMR spectroscopic data for compounds L1, 5, 7 and 9
Entry
L1
31
P-{1H} NMR
P (CDCl3, ppm) J (Hz)
43.82 (s)
1
H (ppm, CDCl3)
8.33 (s, 1H, C2-H)
7.55 (s, 1H, C8-H)
7.31-7.29 (m, 10H, ArH)
5.57 (br s, 2H, NH2)
4.17 (t, 2H, AdeCH2CH2)
3.47 (m, 2H, AdeCH2CH2 )
2.20 (br dt, 1H, NH)
5*
25.01 (s)
13
H NMR
8.25 (s, 1H, C2-H)
7.96 (s, 1H, C8-H)
7.76-7.38 (m, 10H, ArH)
5.67 (br s, 2H, NH2)
4.60 (q, 1H, NH)
J (Hz)
3
JCHCH = 6
JCHCH = 6
3
JNHCH = 7
3
JPNCH = 10
2
JPNH = 4
3
JNHCH = 7
3
2
JPNH = 7
JCHNH = 7
3
JCHCH = 6
3
JCHCH = 6
3
JCHNH = 7
3
JPNCH = 11
3
4.33 (t, 2H, AdeCH2CH2)
3.32 (m, 2H, AdeCH2CH2 )
C-{1H} NMR
C (ppm, CDCl3)
J (Hz)
155.31 (C6)
152.89 (C2)
150.14 (C4)
140.92 (C8)
119.71 (C5)
46.18 (d, AdeCH2CH2)
45.93 (d, AdeCH2CH2)
140.77 (s, ArCi)
131.18 (d, ArCo)
128.57 (d, ArCm)
128.28 (s, ArCp)
3
155.65 (C6)
152.67 (C2)
150.06 (C4)
141.68 (C8)
119.69 (C5)
45.63 (d, AdeCH2CH2)
40.48 (AdeCH2CH2)
132.07 (d, ArCi)
131.86 (d, ArCo)
131.81 (d, ArCp)
128.44 (d, ArCm)
3
JPC = 6
JPC = 17
2
2
JPC = 20
JPC = 25
3
JPC = 6
1
JPC = 128
JPC = 9
4
JPC = 3
3
JPC = 12
2
Supplementary Material (ESI) for Dalton Transactions
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7
9
8.21 (s, 1H, C2-H)
7.84 (s, 1H, C8-H)
7.85-7.35 (m, 10H, ArH)
5.70 (br s, 2H, NH2)
4.43 (t, 2H, AdeCH2CH2)
3.59 (q, 1H, NH)
3.32 (m, 2H, AdeCH2CH2 )
60.69 (s)
57.03 (s)
1
JP-Se =
753
8.10 (s, 1H, C2-H)
7.86 (s, 1H, C8-H)
7.72-7.24 (m, 10H, ArH)
6.07 (br s, 2H, NH2)
4.46 (dt, 1H, NH)
3
JCHCH = 6
JPNH = 7
3
JCHNH = 7
3
JPNCH = 12
2
2
JPNH = 5
JNHCH = 7
3
JCHCH = 5
3
JNHCH = 7
3
JPNCH = 12
3
4.35 (t, 2H, AdeCH2CH2)
3.31 (m, 2H, AdeCH2CH2 )
* In CDCl3 + several drops of DMSO-d6
155.40 (C6)
152.80 (C2)
150.27 (C4)
141.16 (C8)
119.75 (C5)
43.98 (d, AdeCH2CH2)
41.37 (s, AdeCH2CH2)
134.07 (d, ArCi)
131.80 (d, ArCp)
131.34 (d, ArCo)
128.50 (d, ArCm)
3
155.66 (C6)
152.67 (C2)
150.20 (C4)
141.37 (C8)
119.65 (C5)
44.94 (d, AdeCH2CH2)
41.88 (s, AdeCH2CH2)
134.49(d, ArCi)
131.72 (d, ArCp)
131.50 (d, ArCo)
128.29 (d, ArCm)
3
JPC = 7
1
JPC = 100
JPC = 3
2
JPC = 13
3
JPC = 13
4
JPC = 8
1
JPC = 91
JPC = 3
2
JPC = 12
3
JPC = 12
4
Supplementary Material (ESI) for Dalton Transactions
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Table S3 NMR spectroscopic data for L2, 6, 8 and 10
Entry
L2
31
P-{1H} NMR
P (CDCl3, ppm) J (Hz)
1
H NMR
H (CDCl3, ppm)
62.83 (s)
8.34 (s, 1H, C2-H)
7.42 (s, 1H, C8-H)
7.35 (m, 10H, ArH)
5.61 (br s, 2H, NH2)
4.01 (t, 2H, AdeCH2CH2)
3.52 (dt, 2H, AdeCH2CH2 )
3.02 (m, 2H, CH2CH2CH3)
1.44 (sxt, 2H, CH2CH2CH3)
0.73 (t, 3H, NCH2CH2CH3)
6
32.51 (s)
8.27 (s, 1H, C2-H)
7.78 (s, 1H, C8-H)
7.73-7.36 (m, 10H, ArH)
5.87 (br s, 2H, NH2)
4.36 (t, 2H, AdeCH2CH2)
3.50 (dt, 2H, AdeCH2CH2 )
2.88 (m, 2H, CH2CH2CH3)
1.51 (sxt, 2H, CH2CH2CH3)
0.69 (t, 3H, NCH2CH2CH3)
13
J (Hz)
3
JCHCH = 6
JCHCH = 6
3
JPNCH = 3
3
3
3
JCHCH = 7
JCHCH = 7
3
JCHCH = 6
JCHCH = 6
3
JPNCH = 11
3
3
3
JCHCH = 7
JCHCH = 7
C-{1H} NMR
C (CDCl3, ppm)
155.34 (C6)
152.81 (C2)
149.93 (C4)
140.65 (C8)
119.55 (C5)
42.81 (d, AdeCH2CH2)
50.15 (AdeCH2CH2)
54.27 (d, NCH2CH2CH3)
22.73 (d, NCH2CH2CH3)
11.29 (s, NCH2CH2CH3)
139.19 (d, ArCi)
132.93 (d, ArCo)
128.49 (d, ArCm)
128.21(s, ArCp)
155.30 (C6)
152.76 (C2)
150.16 (C4)
141.16 (C8)
119.68 (C5)
43.01 (d, AdeCH2CH2)
45.27 (d, AdeCH2CH2)
49.01 (d, NCH2CH2CH3)
21.84 (d, NCH2CH2CH3)
11.21 (s, NCH2CH2CH3)
132.26 (d, ArCi)
132.08 (d, ArCo)
128.55 (d, ArCm)
131.95 (d, ArCp)
J (Hz)
3
JPC = 3
JPC = 11
2
JPC = 17
3
JPC = 3
2
1
JPC = 14
JPC = 20
3
JPC = 25
2
3
JPC = 7
JPC = 3
2
JPC = 3
3
JPC = 3
2
1
JPC = 127
JPC = 10
3
JPC = 12
4
JPC = 3
2
Supplementary Material (ESI) for Dalton Transactions
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8
8.28 (s, 1H, C2-H)
7.63 (s, 1H, C8-H)
7.88-7.35 (m, 10H, ArH)
5.83 (br s, 2H, NH2)
4.33 (t, 2H, AdeCH2CH2)
3.53 (dt, 2H, AdeCH2CH2 )
70.52 (s)
3.04 (m, 2H, CH2CH2CH3)
1.63 (sxt, 2H, NCH2CH2CH3)
0.82 (t, 3H, NCH2CH2CH3)
10
69.28 (s)
1
JP-Se = 755
8.28 (s, 1H, C2-H)
7.64 (s, 1H, C8-H)
7.89-7.35 (m, 10H, ArH)
6.11 (br s, 2H, NH2)
4.34 (t, 2H, AdeCH2CH2)
3.52 (dt, 2H, AdeCH2CH2 )
2.95 (m, 2H, NCH2CH2CH3)
1.58 (sxt, 2H, NCH2CH2CH3)
0.72 (t, 3H, NCH2CH2CH3)
3
JCHCH = 7
JCHCH = 7
3
JPNCH = 12
3
3
3
JCHCH = 7
JCHCH = 7
3
JCHCH = 7
JCHCH = 7
3
JPNCH = 13
3
3
3
JCHCH = 7
JCHCH = 7
155.38 (C6)
152.99 (C2)
150.00 (C4)
140.67 (C8)
119.47 (C5)
42.43 (d, AdeCH2CH2)
45.92 (d, AdeCH2CH2)
49.96 (d, NCH2CH2CH3)
21.58 (d, NCH2CH2CH3)
11.32 (s, NCH2CH2CH3)
132.85 (d, ArCi)
131.95 (d, ArCo)
128.40 (d, ArCm)
131.74 (d, ArCp)
155.50 (C6)
152.85 (C2)
149.93 (C4)
140.51 (C8)
119.44 (C5)
42.07 (d, AdeCH2CH2)
46.62 (d, AdeCH2CH2)
50.52 (d, NCH2CH2CH3)
21.43 (d, NCH2CH2CH3)
11.32 (s, NCH2CH2CH3)
132.30 (d, ArCi)
132.14 (d, ArCo)
128.54 (d, ArCm)
131.84 (d, ArCp)
3
JPC = 4
JPC = 4
2
JPC = 2
3
JPC = 5
2
1
JPC = 95
JPC = 11
3
JPC = 13
4
JPC = 3
2
3
JPC = 4
JPC = 4
2
JPC = 2
3
JPC = 5
2
1
JPC = 92
JPC = 12
3
JPC = 13
4
JPC = 3
2
Supplementary Material (ESI) for Dalton Transactions
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Table S4 Comparison of the proton and carbon signals of the two
methylene groups of compounds L1, L2, 5-10 and 1-4
L1
5
7
9
L2
6
8
10
1
2
3
4
AdeCH2CH2
(H, ppm)
4.17
4.33
4.43
4.35
4.01
4.36
4.33
4.34
4.48
4.36
4.18
4.30
AdeCH2CH2
(H, ppm)
3.47
3.32
3.32
3.31
3.52
3.50
3.53
3.52
3.88
3.82
3.09
3.09
AdeCH2CH2
(C, ppm)
46.18
45.63
43.98
44.94
42.81
43.01
42.43
42.07
44.98
43.25
41.11
42.91
AdeCH2CH2
(C , ppm)
45.93
40.48
41.37
41.88
50.15
45.27
45.92
46.62
41.84
50.39
46.40
48.29
Table S5 Selected bond lengths (Å) and angles (°) in compound 5
P(1)-O(1)
P(1)-C(13)
N(12)-C(11)
C(10)-N(9)
C(8)-N(7)
C(5)-C(4)
N(3)-C(2)
N(1)-C(6)
C(6)-C(5)
1.484(8)
1.777(12)
1.476(12)
1.458(13)
1.345(13)
1.378(14)
1.293(14)
1.327(14)
1.372(14)
P(1)-N(12)
P(1)-C(19)
C(11)-C(10)
N(9)-C(8)
N(7)-C(5)
C(4)-N(3)
C(2)-N(1)
C(6)-N(6)
1.656(9)
1.792(12)
1.465(15)
1.371(14)
1.412(18)
1.339(14)
1.344(14)
1.351(13)
O(1)-P(1)-N(12)
O(1)-P(1)-C(19)
C(13)-P(1)-N(12)
C(13)-P(1)-N(12)
P(1)-N(12)-C(11)
C(10)-N(9)-C(8)
C(4)-N(9)-C(8)
C(8)-N(7)-C(5)
115.5(5)
113.8(5)
105.0(5)
105.0(5)
117.0(7)
126.5(11)
105.4(9)
102.8(10)
O(1)-P(1)-C(13)
C(13)-P(1)-C(19)
C(13)-P(1)-N(12)
C(19)-P(1)-N(12)
N(12)-C(11)-C(10)
C(10)-N(9)-C(4)
N(9)-C(8)-N(7)
N(7)-C(5)-C(4)
111.0(5)
106.5(5)
105.0(5)
104.2(5)
110.2(10)
127.5(10)
114.3(11)
111.4(11)
Supplementary Material (ESI) for Dalton Transactions
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C(5)-C(4)-N(9)
N(3)-C(2)-N(1)
N(1)-C(6)-C(5)
C(5)-C(6)-N(6)
N(7)-C(5)-C(6)
106.0(10)
129.8(13)
117.8(11)
121.8(10)
133.0(12)
C(4)-N(3)-C(2)
C(2)-N(1)-C(6)
C(6)-C(5)-C(4)
N(6)-C(6)-N(1)
108.3(11)
119.1(12)
115.7(11)
120.4(12)
Table S6 NMR spectroscopic data for complexes of L1
Entry
11a
31
P-{1H} NMR
J (Hz)
P (CDCl3, ppm)
1
H NMR
H (CDCl3, ppm)
8.09 (s, 1H, C2-H)
7.76 (s, 1H, C8-H)
7.41-7.26 (m, 10H, ArH)
6.04 (br s, 2H, NH2)
4.86 (q, 1H, NH)
63.58 (s)
J (Hz)
3
JNHCH = 6
JPCH = 6
3
JCHCH = 6
3
JCHCH = 6
3
JNHCH = 6
3
JPNCH = 10
2
4.24 (t, 2H, AdeCH2CH2)
3.42 (m, 2H, AdeCH2CH2 )
13b
63.77 (d)
1
JPRh = 158
8.16 (s, 1H, C2-H)
7.86 (s, 1H, C8-H)
7.51-7.26 (m, 10H, ArH)
5.73 (br s, 2H, NH2)
5.46 (br s, 2H, CH of cod)
4.08 (m, 3H, NH + AdeCH2CH2)
3.08 (quint, 2H, AdeCH2CH2 )
3
JCHCH = 6
JNHCH = 6
3
JPNCH = 6
3
2.83 (br s, 2H, CH of cod)
2.52-1.80 (br m, 8H, CH2 of cod)
15
69.40 (d)
1
JP-Rh = 149
8.15 (s, 1H, C2-H)
8.05 (s, 1H, C8-H)
7.73-7.28 (m, 10H, ArH)
6.04 (br s, 2H, NH2)
3.97 (t, 2H, AdeCH2CH2)
3.62 (dt, 1H, NH)
3.05 (m, 2H, AdeCH2CH2 )
1.35 (d, 15H, CH3 of Cp*)
3
JCHCH = 5
JNHCH = 7
2
JNHP = 13
3
JNHCH = 7
3
JCHCH = 5
3
JPNCH = 7
4
JPCH = 4
3
Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2003
17
8.16 (s, 1H, C2-H)
8.04 (s, 1H, C8-H)
7.66-7.26 (m, 10H, ArH)
5.92 (br s, 2H, NH2)
4.00 (t, 2H, AdeCH2CH2)
3.77 (dt, 1H, NH)
37.74 (s)
3.05 (m, 2H, AdeCH2CH2 )
1.35 (d, 15H, CH3 of Cp*)
19
20
8.34 (s, 1H, C2-H)
7.85 (s, 1H, C8-H)
7.65-7.27 (m, 10H, ArH)
5.74 (br s, 2H, NH2)
5.05(br m, 2H, of C10H16)
4.29 (m + t, 3H, NH + AdeCH2CH2)
3.94 (d, 2H, of C10H16)
3.41 (t, 2H, of C10H16)
3.11 (m, 2H, AdeCH2CH2 )
2.93 (d, 2H, of C10H16)
2.65 (m, 2H, of C10H16)
2.10 (m, 6H, of C10H16)
55.25 (s)
8.12 (s, 1H, C2-H)
7.95 (s, 1H, C8-H)
7.59-7.28 (m, 10H, ArH)
5.94 (br s, 2H, NH2)
5.27 (d, 2H, ArH of p-MeC6H4iPr)
5.06 (d. 2H, ArH of p-MeC6H4iPr)
3.88 (t, 2H, AdeCH2CH2)
3.39 (dt, 1H, NH)
64.23 (s)
3.05 (m, 2H, AdeCH2CH2 )
2.53 (sep, 1H, CH of iPr)
1.92 (s, 3H, CH3 of p-MeC6H4iPr)
0.77 (d, 6H, CH3 of iPr)
21
1
60.60 (d)
JPPt =
2106
8.09 (s, 1H, C2-H)
7.84 (s, 1H, C8-H)
7.30-7.24 (m, 24H, NH2 + ArH)
4.04 (t, 4H, AdeCH2CH2)
3.83 (br q, 2H, NH)
3.09 (br m, 4H, AdeCH2CH2 )
0.73 (br s, 6H, CH3)
a
in CDCl3 + drops of DMSO-d6,
b
in CD2Cl2
3
JCHCH = 5
JNHCH = 8
2
JNHP = 12
3
JNHCH = 8
3
JCHCH = 5
3
JPNCH = 6
4
JPCH = 3
3
3
JCHCH = 6
3
JCHCH = 6
JCHCH = 6
3
JCHCH = 5
3
JNHCH = 7
2
JNHP = 14
3
JCHCH = 5
3
JNHCH = 7
3
JPNCH = 7
3
JCHCH = 6
3
JCHCH = 6
3
3
JCHCH = 6
JNHCH = 6
2
JNHP = 6
3
2
JPtCH = 33
Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2003
Table S7 NMR spectroscopic data for the complexes of L2
Entry
12
14
31
P-{1H} NMR
J (Hz)
P (CDCl3, ppm)
H NMR
H(CDCl3, ppm)
8.13 (s, 1H, C -H)
7.59 (s, 1H, C8-H)
7.41-7.29 (m, 10H, ArH)
6.01 (br s, 2H, NH2)
4.15 (t, 2H, AdeCH2CH2)
3.70 (dt, 2H, AdeCH2CH2 )
3.13 (m, 2H, NCH2CH2CH3)
1
JRh-P = 161
1.44 (sxt, 2H, NCH2CH2CH3)
0.68 (t, 3H, NCH2CH2CH3)
8.36 (s, 1H, C2-H)
8.07 (s, 1H, C8-H)
7.66-7.34 (m, 10H, ArH)
5.66 (br s, 2H, NH2)
4.51 (t, 2H, AdeCH2CH2)
4.13 (dt, 2H, AdeCH2CH2 )
3.28 (q, 2H, NCH2CH2CH3)
1.58 (sxt, 2H, NCH2CH2CH3)
0.77 (t, 3H, NCH2CH2CH3)
5.57 (br s, 2H, CH of cod)
2.97 (br s, 2H, CH of cod)
2.37-1.60 (br m, 8H, CH2 of cod)
16
18
80.30 (br d)
48.96 (s)
J (Hz)
2
79.51 (s)
82.22 (d)
1
1
JRh-P = 152
3
JCHCH = 6
JCHCH = 6
3
JPNCH = 12
3
3
JCHCH = 7
3
JCHCH = 7
JCHCH = 7
3
JPNCH = 10
3
JCHCH = 7
3
JPNCH = 7
3
JCHCH = 7
3
JCHCH = 7
3
Too broad and complicated to be
assigned
8.28 (s, 1H, C2-H)
8.15 (br s, 1H, C8-H)
7.90 (br s, 4H, ArH)
7.41 (br s, 6H, ArH)
5.62 (br s, 2H, NH2)
4.23 (br s, 2H, AdeCH2CH2)
3.77 (br s, 2H, AdeCH2CH2 )
2.90 (br s, 2H, NCH2CH2CH3)
1.75 (br s, 2H, NCH2CH2CH3)
0.85 (br s, 3H, NCH2CH2CH3)
1.23 (d, 15H, CH3 of Cp*)
4
JPCH = 2
Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2003
22
59.92 (s)
1
JPt-P = 3983
8.24 (s, 2H, C2-H)
7.66 (s, 2H, C8-H)
7.52-7.05 (m, 20H, ArH)
5.92 (br s, 4H, NH2)
4.07 (t, 4H, AdeCH2CH2)
3.78 (sl br dt, 4H, AdeCH2CH2 )
3.09 (sl br dt, 4H, NCH2CH2CH3)
1.28 (sl br sxt, 4H,NCH2CH2CH3)
0.59 (t, 6H, NCH2CH2CH3)
3
JCHCH = 7
JCHCH = 7
3
JPNCH = 9
3
JCHCH = 7
3
JPNCH = 9
3
JCHCH = 7
3
JCHCH = 7
3
Table S8 Comparative bond lengths (Å) and angles (°) in compound 11, 15 and 17
Compounds
P(1)-M(1)
M (1)-Cl(1)
M(1)-Cl(2)
P(1)-N(12)
P(1)-C(13)
P(1)-C(19)
N(12)-C(11)
C(11)-C(10)
C(10)-N(9)
N(9)-C(8)
C(8)-N(7)
N(7)-C(5)
C(5)-C(4)
C(4)-N(3)
N(3)-C(2)
C(2)-N(1)
N(1)-C(6)
C(6)-N(6)
C(6)-C(5)
P(1)-M(1)-Cl(1)
Cl(1)-M(1)-Cl(2)
P(1)-M(1)-Cl(2)
M(1)-P(1)-N(12)
M(1)-P(1)-C(13)
M(1)-P(1)-C(19)
C(13)-P(1)-C(19)
C(13)-P(1)-N(12)
C(19)-P(1)-N(12)
P(1)-N(12)-C(11)
N(12)-C(11)-C(10)
C(10)-N(9)-C(8)
C(10)-N(9)-C(4)
C(4)-N(9)-C(8)
N(9)-C(8)-N(7)
C(8)-N(7)-C(5)
N(7)-C(5)-C(4)
11
2.2259(18)
1.2826(17)
1.644(7)
1.820(9)
1.798(7)
1.420(9)
1.494(10)
1.476(8)
1.349(8)
1.296(8)
1.383(8)
1.357(8)
1.348(7)
1.321(8)
1.334(8)
1.346(8)
1.321(8)
1.410(9)
176.62(8)
114.2(2)
112.8(3)
110.3(2)
105.2(4)
107.4(3)
106.4(4)
126.8(4)
114.8(5)
127.7(5)
127.7(5)
104.6(5)
115.3(6)
103.1(5)
110.0(6)
15
2.3328(10)
2.4102(11)
2.4124(11)
1.662(3)
1.817(4)
1.826(4)
1.453(5)
1.511(6)
1.459(5)
1.351(6)
1.322(6)
1.392(5)
1.389(6)
1.337(6)
1.324(7)
1.333(7)
1.344(6)
1.351(6)
1.385(6)
17
2.293(3)
2.395(3)
2.405(3)
1.624(9)
1.876(10)
1.835(9)
1.511(12)
1.504(14)
1.401(12)
1.393(7)
1.395(14)
1.37(2)
1.373(16)
1.344(16)
1.330(15)
1.349(15)
1.23(2)
1.439(15)
1.42(2)
86.35(4)
89.80(4)
91.59(4)
107.78(12)
119.78(14)
112.08(13)
104.22(18)
104.46(18)
107.76(17)
127.8(3)
111.5(3)
127.5(4)
126.5(4)
105.9(4)
114.4(4)
103.6(4)
110.3(4)
88.85(10)
87.26(10)
88.28(10)
111.2(2)
112.5(3)
118.4(4)
102.0(5)
104.4(4)
107.1(5)
125.7(6)
112.5(9)
126.3(12)
127.7(12)
105.9(11)
109.1(13)
107.1(13)
109.8(17)
Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2003
C(5)-C(4)-N(9)
C(4)-N(3)-C(2)
N(3)-C(2)-N(1)
C(2)-N(1)-C(6)
N(1)-C(6)-C(5)
C(6)-C(5)-C(4)
C(5)-C(6)-N(6)
N(6)-C(6)-N(1)
N(7)-C(5)-C(6)
106.0(5)
109.9(5)
130.2(6)
118.0(5)
117.4(6)
117.3(5)
123.1(5)
119.5(6)
131.6(6)
105.7(4)
110.0(4)
130.6(5)
117.2(4)
118.7(4)
117.1(4)
121.8(4)
119.5(4)
132.6(4)
110.6(5)
110.6(5)
127.6(6)
119.2(5)
120.1(6)
118.4(6)
121.1(5)
118.6(5)
135.4(5)