4238 Inorganic Chemistry, Vol. 36, No. 19, 1997
Kaiwar et al.
purchased from EM Science, Cherry Hill, NJ, and treated with 6% H2O
by weight to generate the Brockmann activity 3 material used
throughout this study.
(dppe)Pt{S2C2(2-quinoxaline)(Me)} (27) was prepared and isolated
as described for complex 24, using (dppe)Pt(SH)2 (132 mg, 0.20 mmol)
and 1-quinoxalin-2-yl-2-bromopropanone (56 mg, 0.22 mmol). Com-
plex 27 was obtained as an orange red crystalline solid in 49% yield
(81 mg, 0.098 mmol). Anal. Calcd for C37H32N2P2PtS2: C, 53.82; H,
3.88; N, 3.39. Found: C, 54.12; H, 4.09; N, 3.15. 1H NMR (CDCl3):
δ 9.14 (s, 1H, C8H5N2), 7.98 (d, 1H, C8H5N2, JH-H ) 7 Hz), 7.95 (d,
1H, C8H5N2, JH-H ) 7 Hz), 7.88-7.76 (m, 8H, PC6H5), 7.71-7.63
(m, 2H, C8H5N2), 7.53-7.48 (m, 12H, PC6H5), 2.53 (d, 4H, PCH2,
JP-H ) 18 Hz; JPt-H ) 54 Hz), 2.39 (s, 3H, CH3). 31P NMR (CDCl3):
δ 45.1 (d with Pt satellites, JP-P ) 15 Hz; JPt-P ) 2780 Hz), 44.7 (d
with Pt satellites, JP-P ) 15 Hz; JPt-P ) 2756 Hz). Mass spectrum
(FAB) m/z ) 826 (M+), 627 (M+ - C11H8N2S). UV-vis (abs) λmax
(ꢀ) (CH2Cl2, nm): 248 (23 500), 270 (25 100), 310 (14 600), 328
(13 300) 461 (4300). IR (KBr, cm-1): 3038 (w), 2923 (w), 2846 (w),
1511 (s), 1489 (m), 1436 (vs), 1412 (w), 1339 (w), 1301 (w), 1268
(w), 1202 (m), 1136 (w), 1103 (s), 1027 (w), 998 (m), 938 (w), 880
(m) 824 (m), 750 (m), 748 (m), 714 (s), 691 (vs), 531 (vs), 484 (m).
Physical Measurements. NMR spectra were acquired with a Bru¨ker
AF 200 or a Bru¨ker AM 400. IR spectra were collected either with a
Perkin Elmer 1600 or a Nicolet 5 DXL FT-IR spectrometer. UV-
visible spectra were recorded on either a Perkin Elmer Lambda 2S or
a Hewlett Packard 8452A spectrometer. EI and FAB mass spectral
data were collected on a Magnetic Sector VG 7070E. Chemical
analyses were performed by M-H-W Laboratories, Phoenix, AZ.
Synthesis. (dppe)Ni{S2C2(2-quinoxaline)(H)}‚CH2Cl2 (24). To
a DMF (5 mL) solution of (dppe)Ni(SH)2 (314 mg, 0.60 mmol) was
added 1-quinoxalin-2-yl-2-bromoethanone (150 mg, 0.62 mmol). The
solution became purple over a period of 20 min. The DMF was
removed from the resulting purple solution, and the solid was washed
with 3 × 20 mL of diethyl ether. The purple solid was dissolved in
dichloromethane (5 mL), and triethylamine was added dropwise to the
solution until it was orange red. The solvent was removed in air, and
the solid was chromatographed on a 1 × 20 cm alumina column, where
the product eluted with 1:2 hexane-CH2Cl2. The eluent was evaporated
to dryness to give 24 as an orange-red crystalline solid in 43% yield
(190 mg, 0.26 mmol). Anal. Calcd for C37Cl2H32N2P2S2Ni: C, 58.42;
H, 4.21; N, 3.68. Found: C, 58.82; H, 4.49; N, 3.49. 1H NMR
(CDCl3): δ 9.27 (s, 1H, C8H5N2), 7.94 (d, 1H, S2C2H, JP-H ) 8 Hz),
7.90 (d, 1H, C8H5N2, JH-H ) 8 Hz), 7.88 (d, 1H, C8H5N2, JH-H ) 8
Hz), 7.82-7.77 (m, 8H, PC6H5), 7.61-7.54 (m, 2H, C6H4N2), 7.51-
7.44 (m, 12H, PC6H5), 2.39 (d, 4H, PC2H2, JP-H ) 18 Hz). 31P NMR
(CDCl3): δ 58.5 (broad s), 58.2 (broad s). Mass spectrum (FAB) m/z
) 675 (M+), 456 (M+ - C10H6N2S2). UV-vis (abs) λmax (ꢀ) (CH2Cl2,
nm): 240 (24 927), 276 (20 223) 302 (16 000), 346(sh) (6000), 444
(5700), 580 (90). IR (KBr, cm-1): 3052 (w), 2946 (w), 2903 (w),
1540 (m), 1506 (vs), 1475 (m), 1435 (vs), 1406 (w), 1330 (w), 1301
(w), 1284 (w), 1265 (w), 1207 (m), 1187 (w), 1129 (w), 1099 (s), 1027
(w), 999 (m), 922 (w), 876 (m) 830 (w), 818 (m), 761 (w), 746 (m),
713 (s), 690 (vs), 530 (vs), 484 (m).
(dppe)Ni{S2C2(2-pyridine)(H)} (28) was prepared and isolated as
described for complex 24, using 1-pyridin-2-yl-2-bromoethanone (0.025
g, 0.125 mmol) and (dppe)Ni(SH)2 (0.052 g, 0.1 mmol). Complex 28
was isolated as a green solid in 29% yield (0.018 g, 0.029 mmol). Anal.
Calcd for C33H29NNiP2S2: C, 63.46; H, 4.65; N, 2.24. Found: C, 63.33;
H, 4.52; N, 1.93. 1H NMR (CDCl3) δ 8.36 (d, 1H, C5H4 N, JH-H ) 4
Hz), 7.99 (d, 1H, S2C2H, JP-H ) 6 Hz), 7.80-7.71 (m, 8H, PC6H5),
7.66 (d, 1H, C5H4N, JH-H ) 6 Hz), 7.50 (m, 1H, C5H4 N), 7.46-7.40
(m, 12H, PC6H5), 6.85 (m, 1H, C5H4 N), 2.37 (m, 2H, PC2H2), 2.33
(m, 2H, PC2H2). 31P NMR (CDCl3): δ 57.4 (broad singlet), 57.2 (broad
singlet). Mass spectrum (FAB) m/z ) 624 (M+), 489 (M+ - C7H5-
NS2). UV-vis (abs) λmax (ꢀ) (CH2Cl2, nm): 367 (4540), 584 (90). IR
(KBr, cm-1): 3050 (w), 2962 (w), 2908 (w), 1578 (m), 1508 (m), 1482
(m), 1459 (vs), 1436 (vs), 1420 (m), 1313 (w), 1262 (m), 1189 (vs),
1174 (s), 1119(s), 1102 (vs), 1070 (m), 1026 (m), 998 (m), 932 (w),
881 (w), 796 (m), 735 (vs), 715 (s), 692 (vs), 622 (s), 611 (s), 543
(m), 532 (m), 514 (s), 501(s), 484 (m).
(dppe)Pd{S2C2(2-quinoxaline)(H)} 25 was prepared and isolated
as described for complex 24, using (dppe)Pd(SH)2 (342 mg, 0.60 mmol)
and 1-quinoxalin-2-yl-2-bromoethanone (150 mg, 0.62 mmol). Com-
plex 25 was isolated in 53% yield (230 mg, 0.32 mmol). Anal. Calcd
for C36H30N2P2PdS2: C, 59.83; H, 4.16; N, 3.88. Found: C, 59.72; H,
4.37; N, 3.89. 1H NMR (CDCl3): δ 9.32 (s, 1H, C8H5N2), 7.99 (d,
1H, S2C2H, JP-H ) 8 Hz), 7.97 (d, 1H, C8H5N2, JH-H ) 8 Hz), 7.85
(d, 1H, C8H5N2, JH-H ) 8 Hz), 7.83-7.76 (m, 8H, PC6H5), 7.50-7.47
(m, 2H, C8H5 N2), 7.47-7.42 (m, 12H, PC6H5), 2.51 (d, 4H, PC2H2,
JP-H ) 21 Hz). 31P NMR (CDCl3): δ 51.4 (d, JP-P ) 15 Hz), 51.2 (d,
(dppe)Pd{S2C2(2-pyridine)(H)} (29) was prepared and isolated as
described for complex 24, using (dppe)Pd(SH)2 (0.057 g, 0.1 mmol)
and 1-pyridin-2-yl-2-bromoethanone (0.025 g, 0.125 mmol). Complex
29 was isolated as a pink crystalline solid in 31% yield (21 mg, 0.03
mmol). Anal. Calcd for C33H29NP2PdS2: C, 58.98; H, 4.32; N, 2.09.
Found: C, 58.69; H, 4.61; N, 1.92. 1H NMR (CDCl3): δ 8.38 (m,
1H, C5H4 N), 8.00 (dd, 1H, S2C2H, JP-H ) 6 Hz; JP-H ) 1 Hz), 7.86-
7.76 (m, 8H, PC6H5), 7.73 (d, 1H, C5H4 N, JH-H ) 8 Hz), 7.60 (m,
1H, C5H4 N), 7.54-7.49 (m, 12H, PC6H5), 6.99 (m, 1H, C5H4 N), 2.59
(m, 2H, PC2H2), 2.53 (m, 2H, PC2H2). 31P NMR (CDCl3): δ 50.7 (d,
JP-P ) 15 Hz), 50.2 (d, JP-P ) 15 Hz). Mass spectrum (FAB) m/z )
672 (M+), 504 (M+ - C7H5NS2). UV-vis (abs) λmax (ꢀ) (CH2Cl2,
nm): 298 (5800), 360 (4000), 519 (90). IR (KBr, cm-1): 3046 (w),
2966 (w), 2912 (w), 2877(w), 1578 (m), 1523 (m), 1482 (m), 1459
(m), 1435 (vs), 1406 (w), 1330 (w), 1301 (w), 1284 (w), 1265 (w),
1207 (w), 1186 (w), 1159 (w), 1102 (s), 1026 (w), 997 (m), 930 (w),
877 (m), 820 (m), 761 (w), 746 (m), 715 (s), 704 (s), 690 (vs), 530
(vs), 484 (m).
JP-P ) 15 Hz). Mass spectrum (FAB) m/z ) 723 (M+), 506 (M+
-
C10H6N2S2). UV-vis (abs) λmax (ꢀ) (CH2Cl2, nm): 240 (21 000), 281
(15 500), 308 (11 500), 342 (5200), 443 (5300), 520 (80). IR (KBr,
cm-1): 3048 (w), 2947 (w), 2903 (w), 1540 (m), 1504 (vs), 1477 (m),
1435 (vs), 1412 (w), 1330 (w), 1306 (w), 1284 (w), 1265 (w), 1207
(m), 1187 (w), 1130 (w), 1102 (s), 1027 (w), 999 (m), 920 (w), 877
(m) 855 (w), 821 (m), 799 (w), 761 (w), 748 (m), 714 (s), 690 (vs),
530 (vs), 484 (m).
(dppe)Pt{S2C2(2-quinoxaline)(H)}‚CH2Cl2 (26) was prepared and
isolated as described for complex 24, using (dppe)Pt(SH)2 (132 mg,
0.20 mmol) and 1-quinoxalin-2-yl-2-bromoethanone (53 mg, 0.21
mmol). Complex 26 was isolated in 40% yield (70 mg, 0.080 mmol).
Anal. Calcd for C37H32Cl2N2PtP2S2: C, 49.55; H, 3.57; N, 3.13.
Found: C, 49.88; H, 3.31; N, 3.07. 1H NMR (CDCl3): δ 9.33 (s, 1H,
(dppe)Pt{S2C2(2-pyridine)(H)} (30) was prepared and isolated as
described for complex 24, using (dppe)Pt(SH)2 (0.165 g, 0.25 mmol)
and 1-pyridin-2-yl-2-bromoethanone (0.062 g, 0.313 mmol). Complex
30 was isolated as a yellow crystalline solid in 41% yield (78 mg,
0.10 mmol). Anal. Calcd for C33H29NP2PtS2: C, 52.04; H, 3.81; N,
1.84. Found: C, 51.88; H, 4.09; N, 1.57. 1H NMR (CDCl3): δ 8.38
(m, 1H, C5H4 N), 7.96 (dd with 195Pt satellites, 1H, S2C2H, JP-H ) 7
Hz; JP-H ) 1 Hz; JPt-H ) 95 Hz), 7.88-7.79 (m, 8H, PC6H5), 7.69 (d,
1H, C5H4 N, JH-H ) 8 Hz), 7.57 (m, 1H, C5H4 N), 7.52-7.46 (m,
12H, PC6H5), 6.94 (m, 1H, C5H4 N), 2.55 (m, 2H, PC2H2), 2.51 (m,
C8H5N2), 8.35 (d with Pt satellites, 1H, S2C2H, JP-H ) 7 Hz; JPt-H
)
95 Hz), 7.97 (d, 1H, C8H5N2, JH-H ) 7 Hz), 7.89 (d, 1H, C8H5N2, JH-H
) 7 Hz), 7.83-7.77 (m, 8H, PC6H5), 7.58-7.51 (m, 2H, C8H5N2),
7.50-7.44 (m, 12H, PC6H5), 2.51 (d, 4H, PC2H2, JP-H ) 18 Hz; JPt-H
) 55 Hz). 31P NMR(CDCl3): δ 45.7 (d with Pt satellites, JP-P ) 14
2H, PC2H2). 31P NMR (CDCl3): δ 45.5 (d with Pt satellites, JP-P
)
Hz; JPt-P ) 2780 Hz), 45.0 (d with Pt satellites, JP-P ) 14 Hz; JPt-P
)
-
2728 Hz). Mass spectrum (FAB) m/z ) 812 (M+), 594 (M+
15 Hz; JPt-P ) 2770 Hz), 44.9 (d with Pt satellites, JP-P ) 15 Hz;
JPt-P ) 2730 Hz). Mass spectrum (FAB) m/z ) 761 (M+), 593 (M+
- C7H5NS2). UV-vis (abs) λmax (ꢀ) (CH2Cl2, nm): 358 (4300), 415
(sh, 380). IR (KBr, cm-1): 3050 (w), 2963 (w), 2911 (w), 1578 (m),
1522 (m), 1508 (m), 1482 (m), 1459 (m), 1435 (vs), 1310 (w), 1284
(w), 1265 (w), 1207 (m), 1187 (m), 1104 (vs), 1050 (w), 1028 (w),
998 (m), 932 (w), 880 (m), 822 (m), 760 (w), 750 (m), 716 (s), 705(s),
690 (vs), 533 (vs), 486 (m).
C10H6N2S2). UV-vis (abs) λmax (ꢀ) (CH2Cl2, nm): 244 (29 900), 274
(26 800), 306 (8400), 326 (9400), 442 (6000). IR (KBr, cm-1): 3048
(w), 2947 (w), 2915 (w), 2849 (w), 1540 (m), 1506 (vs), 1483 (m),
1435 (vs), 1412 (w), 1330 (w), 1301 (w), 1280 (w), 1265 (w), 1207
(m), 1187 (w), 1131 (w), 1103 (s), 1027 (w), 999 (m), 920 (w), 879
(m) 855 (w), 820 (m), 799 (w), 750 (m), 748 (m), 714 (s), 690 (vs),
531 (vs), 484 (m).