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Helvetica Chimica Acta ± Vol. 84 (2001)
3H2O (1 mmol; Aldrich) in DMF (6 ml; 99,5%; Panreac), LiCl (6.0 mmol; Panreac) was added. The soln. was
refluxed for 5 h (pbbs complex) or 24 h (bpds complex) under Ar. The mixture at r.t. was poured in a beaker and
kept inside a closed container under acetone atmosphere for 3 d. The respective products obtained were filtered
off, washed with cold acetone, and dried at 0.007 Torr for 24 h over P2O5: 4a ´ 4 Na ´ 8H2O ´ 4 LiCl (1.37 g, 88%)
or 4b ´ 4 Na ´ 4H2O ´ 25 LiCl (0.85 g, 42%) as violet microcrystals. UV/VIS Data of 4a ´ 4 Na ´ 4H2O ´ 25 LiCl
(H2O): 465 (11600), 227 (61200). UV/VIS (DMF): 567 (8800), 476 (10300), 282 (70400). IR: 3060, 1640, 1190,
1040. Anal. calc. for C48H28Cl2N4Na4O12RuS4 ´ 8H2O ´ 4 LiCl: C 36.76, H 2.87, N 3.92; found: C 36.99, H 2.85, N
3.59. Data of 4b ´ 4 Na ´ 4H2O ´ 25 LiCl (H2O): 516 (2740), 366 (8750), 301 (14600). (DMF): 564 (7700), 388
(9600), 303 (47100), 250 (24100). Anal. calc. for C20H12Cl2N4Na4O12RuS4 ´ 4H2O ´ 25 LiCl: C 11.51, H 0.87, N
3.22; found: C 11.87, H 1.00, N 2.88.
Heteroleptic Complexes 5 and 6 (Na2[RuL2L']): General Procedure. A mixture of 4a or 4b (1 mmol) and 2a
or 2b (2.0 mmol) in MeOH (40 ml) under Ar was refluxed for 24 h. Different purification procedures were
applied to the mixture (see below).
Disodium Bis[(1,10-phenanthroline-4,7-diyl-kN,kN')bis(benzenesulfonato)(2 )][N-(1,10-phenanthrolin-
5-yl-kN,kN')tetradecanamide]ruthenate(2 ) (5a ´ 2 Na ): The complex was precipitated from the mixture with
acetone/H2O 9 :1, filtered off, washed with Et2O, and purified by prep. TLC (BuOH/AcOH/H2O 7:3 :4). The
fraction containing the pure complex was desorbed with MeOH to yield 5a ´ 2 Na ´ 11 H2SiO3 (0.45 g, 19%).
Orange microcrystals. UV/VIS (H2O): 460 (36600), 427 (35650), 274 (175800). UV/VIS (MeOH): 457 (30000),
430 (28550), 278 (110000). IR: 2940, 2850, 1640, 1570, 1420, 1190, 1050, 810. 1H-NMR (CD3OD): 8.80 (d, J 7.5,
1 H); 8.63 (d, J 9.0, 1 H); 8.55 (br. s, 1 H); 8.44 ± 8.34 (m, 3 H); 8.30 ± 8.20 (m, 6 H); 8.04 (br. s, 2 H); 8.02 ± 7.90
(m, 6 H), 7.76 ± 7.60 (m, 16 H); 2.64 (t, J 6.8, 2 H C(2')); 1.80 (t, J 6.8, 2 H C(3')); 1.47 (m, 2 H C(4'));
1.26 (br. s, 18 H); 0.86 (t, J 6.0, Me). Anal. calc. for C74H63N7Na2O13RuS4 ´ 11 H2SiO3: C 36.81, H 3.23, N 4.21;
found: C 37.15, H 3.48, N 4.10.
Disodium Bis[(1,10-phenanthroline-4,7-diyl-kN,kN')bis(benzenesulfonato)(2 )][N-(1,10-phenanthrolin-
5-yl-kN,kN')acetamide]ruthenate(2 ) (5b ´ 2 Na ). The complex was precipitated from the mixture with
acetone/Et2O 9 :1. The precipitate was filtered off, washed with Et2O, and then precipitated again from MeOH/
Et2O. The product was filtered, washed with CHCl3, and dried at 0.007 Torr over P2O5 overnight: 5b ´ 2 Na ´
8H2O (0.75 g, 50%). Orange microcrystals. UV/VIS (H2O): 459 (22700), 435 (22550), 275 (102000), 215
(98600). IR: 1630, 1550, 1420, 1180, 1050, 840. 1H-NMR (CD3OD): 8.83 (d, J 8.3, 1 H); 8.64 (d, J 8.3, 1 H);
8.56 (br. s, 1 H); 8.46 ± 8.34 (m, 3 H); 8.32 ± 8.23 (m, 6 H); 8.12 ± 7.96 (m, 8 H); 7.88 ± 7.58 (m, 16 H); 2.36 (br. s,
Me). Anal. calc. for C62H39N7Na2O13RuS4 ´ 8H2O: C 49.30, H 3.46, N 6.02; found: C 49.33, H 3.64, N 6.29.
Disodium Bis[(2,2'-bipyridine)-4,4'-disulfonato(2 )-kN,kN'][N-(1,10-phenanthrolin-5-yl-kN,kN')tetra-
decanamide]ruthenate(2 ) (6a ´ 2 Na ). The mixture was filtered and the solid product washed with MeOH,
dried at reduced pressure, and recrystallized from MeOH. Further recovery of the product from the mixture was
achieved by CC (MeOH) followed by reprecipitation with MeOH/MeCN. The product was filtered off, washed
with cold MeCN, and dried at 0.007 Torr over P2O5 for 24 h: 6a ´ 2Na ´ 9 H2O (0.55 g, 41%). Orange
microcrystals. UV/VIS (H2O): 466 (17500), 434 (15600), 296 (67000), 266 (42300), 218 (72000). IR: 2900, 2840,
1620, 1530, 1420, 1220, 1060, 760. 1H-NMR (CD3OD): 9.00 (d, J 1.5, 2 H C(3) of bpds); 8.95 (s, J 1.5,
2 H C(3) of bpds); 8.77 (dd, J 8.4, 1.1, H C(4)); 8.63 (dd, J 8.4, 1.1, H C(7)); 8.52 (s, H C(6)); 8.20 (dd,
J 5.4, 1.1, H C(2)); 8.13 (d, J 5.6, 2 H C(6) of bpds); 8.11 (dd, J 5.4, 1.1, H C(9)); 7.98 (s, 0.5 H,
CONH); 7.96 (s, 0.5 H, CONH); 7.86 (dd, J 8.4, 5.4, H C(3)); 7.84 (dd, J 5.6, 1.5, 2 H C(5) of bpds); 7.80
(dd, J 8.4, 5.4, H C(8)); 7.73 (d, J 5.6, 2 H C(6) of bpds); 7.58 (dd, J 5.6, 1.5, 2 H C(5) of bpds); 2.64 (t,
J 7.0, 2 H C(2')); 1.82 (quint., J 7.0, 2 H C(3')); 1.44 (m, 20 H); 0.89 (t, J 6.3, Me). Anal. calc. for
C46H47N7Na2O13RuS4 ´ 9H2O: C 41.01, H 3.98, N 7.36; found: C 41.13, H 3.88, N 7.30.
Disodium Bis[(2,2'-bipyridine)-4,4'-disulfonato(2 )-kN,kN'][N-(1,10-phenanthrolin-5-yl-kN,kN')acet-
amide]ruthenate(2 ) (6b ´ 2 Na ). The mixture was dissolved in MeOH/H2O 10 :1 and filtered hot to remove
unreacted ligand 2b. The filtrate was evaporated, and the residue reprecipitated from EtOH/H2O. The product
was dried at 0.007 Torr over P2O5 overnight: 6b ´ 2 Na ´ 9H2O (0.93 g, 79%). Orange microcrystals. UV/VIS
(H2O): 466 (16800), 446 (16100), 296 (64500), 264 (44800), 218 (71700). IR: 1620, 1540, 1400, 1220, 1040, 760.
1H-NMR (CD3OD): 8.99 (d, J 1.5, 2 H C(3) of bpds); 8.95 (d, J 1.5, 2 H C(3) of bpds); 8.82 (dd, J 8.4,
1.2, H C(4)); 8.63 (dd, J 8.4, 1.2, H C(7)); 8.54 (s, H C(6)); 8.19 (dd, J 5.1, 1.2, H C(2)); 8.11 (d, J 5.9,
2 H C(6) of bpds); 8.10 (dd, J 5.1, 1.2, H C(9)); 7.97 (s, 0.5 H, CONH); 7.95 (s, 0.5 H, CONH); 7.86 (dd, J
8.4, 5.1, H C(3)); 7.83 (dd, J 5.9, 1.5, 2 H C(5) of bpds); 7.79 (dd, J 8.4, 5.1, H C(8)); 7.72 (d, J 5.9,
2 H C(6) of bpds); 7.57 (dd, J 5.9, 1.5, 2 H C(5) of bpds); 2.36 (s, Me). Anal. calc. for C34H23N7Na2O13RuS4 ´
9H2O: C 34.60, H 3.01, N 8.25; found: C 34.75, H 3.12, N 8.34.