Polynuclear Organometallic Complexes Derived from Ferrocene-Containing Bidentate Ligands
2.10 (s, 6 H), 2.97 (sept, JH,H ϭ 7.0 Hz, 2 H), 4.47 (m, 4 H), 4.58 Synthesis of [{(p-cymene)RuCl(µ-Cl)}2(µ-3)]·CH2Cl2 (10): The pro-
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(m, 4 H), 5.19 (d, JH,H ϭ 3.0 Hz, 4 H), 5.41 (d, JH,H ϭ 3.0 Hz, 4
cedure was similar to that described for the preparation of 4, except
H), 6.86 (m, 4 H), 8.66 (m, 4 H) ppm. IR (KBr): ν˜ ϭ 3045 cmϪ1 that 3 (37 mg, 0.05 mmol) was used instead of 1. The orange solid
(m), 2965 (m), 2872 (m), 1594 (s), 1481 (m), 1417 (m), 1219 (m), of 10 was obtained in a yield of 45% (32 mg). C65H66Cl6Fe2P2Ru2
1110 (m), 1061 (m), 815 (m), 724 (m), 514 (m), 418 (m).
(1435.73): calcd. C 54.37, H 4.63; found C 54.63, H 4.71. 1H NMR
(400 MHz, CDCl3, 25 °C): δ ϭ 0.96 (d, 12 H), 1.75 (s, 6 H), 2.52
(sept, JH,H ϭ 7.0 Hz, 2 H), 3.61 (m, 4 H), 3.89 (m, 4 H), 4.00 (m,
4 H), 4.30 (m, 4 H), 5.07 (s, 8 H), 7.43Ϫ7.37 (m, 12 H), 7.85Ϫ7.80
(m, 8 H) ppm. 31P NMR (160 MHz, CDCl3, 25 °C): δ ϭ
18.99 ppm. IR (KBr): ν˜ ϭ 3044 cmϪ1 (w), 2958 (w), 2868 (w), 1482
(m), 1437 (s), 1384 (m), 1159 (m), 1095 (m), 1032 (s), 825 (s), 742
(s), 694 (s), 540 (m), 517 (s), 472 (s), 450 (s).
Synthesis of [{Cp*RhCl(µ-Cl)}2(µ-1)]·CH2Cl2 (5): The procedure
was similar to that described for the preparation of 4, except that
[Cp*RhCl(µ-Cl)]2 (31 mg, 0.05 mmol) was used instead of [(p-cy-
mene)RuCl(µ-Cl)]2. The orange solid of 5 was obtained in a yield
1
of 95% (47 mg). H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 1.57 (s,
30 H), 4.47(m, 4 H), 4.58 (m, 4 H), 6.92 (m, 4 H), 8.62 (m, 4 H)
ppm. C41H48Cl6FeN2Rh2S2 (1107.35): calcd. C 44.47, H 4.27, N
2.53; found C 44.4, H 4.5, N 2.5. 1H NMR (400 MHz, [D6]DMSO,
Synthesis of [{Cp*RhCl(µ-Cl)}2(µ-3)]·(CH2Cl2)0.5 (11): The proced-
25 °C): δ ϭ 1.66 (s, 30 H), 4.61 (m, 4 H), 4.66 (m, 4 H), 6.93 (m, ure was similar to that described for the preparation of 5, except
4 H), 8.31 (m, 4 H) ppm. IR (KBr): ν˜ ϭ 1636 cmϪ1 (m), 1592 (s), that 3 (37 mg, 0.05 mmol) was used instead of 1. The orange solid
1479 (m), 1417 (m), 1375 (m), 1216 (m), 1109 (m), 1062 (m), 1025
(m), 896 (m), 817 (m), 726 (m), 504 (m), 419 (s).
of 11 was obtained in a yield of 79% (54 mg). C64.5H67Cl5Fe2P2Rh2
(1398.95): calcd. C 55.38, H 4.83; found C 55.8, H 5.0. H NMR
1
(400 MHz, CDCl3, Ϫ60 °C): δ ϭ 1.27 (s, 30 H), 3.93Ϫ3.70 (m, 4
H), 4.28Ϫ4.02 (m, 8 H), 4.50 (m, 4 H), 7.55Ϫ7.30 (m, 12 H),
8.10Ϫ7.82 (m, 8 H) ppm. 31P NMR (160 MHz, CDCl3, 25 °C): δ ϭ
22.33 (d) ppm. IR (KBr): ν˜ ϭ 2359 cmϪ1 (w), 1483 (m), 1434 (s),
1373 (m), 1305 (m), 1192 (m), 1159 (m), 1113 (m), 1094 (m), 1023
(m), 834 (m), 748 (m), 697 (m), 540 (s), 479 (m).
Synthesis of [{Cp*IrCl(µ-Cl)}2(µ-1)] (6): The procedure was similar
to that described for the preparation of 4, except that [Cp*IrCl(µ-
Cl)]2 (39 mg, 0.05 mmol) was used instead of [(p-cymene)RuCl(µ-
Cl)]2. The yellow solid of 6 was obtained in a yield of 87% (51 mg).
C40H46Cl4FeIr2N2S2 (1201.04): calcd. C 40.00, H 3.86, N 2.33;
found C 39.73, H 3.89, N 2.20. 1H NMR (400 MHz, CDCl3, 25
°C): δ ϭ 1.56 (s, 30 H), 4.49 (m, 4 H), 4.58 (m, 4 H), 6.88 (d, Synthesis of [{Cp*IrCl(µ-Cl)}2(µ-3)] (12): The procedure was sim-
1
JH,H ϭ 3.4 Hz, 4 H), 8.61 (d, JH,H ϭ 3.2 Hz, 4 H) ppm. H NMR
(400 MHz, [D6]DMSO, 25 °C): δ ϭ 1.63 (s, 30 H) 4.61 (m, 4 H),
ilar to that described for the preparation of 6, except that 3 (37 mg,
0.05 mmol) was used instead of 1. The orange solid of 12 was ob-
4.67 (m, 4 H), 6.95 (m, 4 H), 8.31 (m, 4 H) ppm. IR (KBr): ν˜ ϭ tained in a yield of 71% (54 mg). C64H66Cl4Fe2Ir2P2 (1535.12):
2917 cmϪ1 (m), 1636 (m), 1595 (s), 1478 (m), 1419 (m), 1380 (m), calcd. C 50.07, H 4.33; found C 49.8, H 4.3. H NMR (400 MHz,
1
1215 (m), 1111 (m), 1061 (m), 1029 (m), 896 (m), 816 (m), 728 (m). CDCl3, Ϫ60 °C): δ ϭ 1.25 (s, 30 H), 3.82Ϫ3.75 (m, 4 H), 4.20Ϫ3.90
(m, 8 H), 4.60Ϫ4.25 (m, 4 H), 7.50Ϫ7.20 (m, 12 H), 8.10Ϫ7.70 (m,
Synthesis of [(p-cymene)RuCl(µ-Cl)}2(µ-2)](7): The procedure was
8 H) ppm. 31P NMR (160 MHz, CDCl3, 25 °C): δ ϭ Ϫ8.53 (s)
similar to that described for the preparation of 4, except that 2
ppm. IR (KBr): ν˜ ϭ 3072 cmϪ1 (w), 2912 (w), 1636 (m), 1435 (s),
(30 mg, 0.05 mmol) was used instead of 1. The orange solid of 7
was obtained in a yield of 52% (31 mg). C50H52Cl4Fe2N2Ru2S2
1374 (m), 1159 (m), 1098 (m), 1085 (m), 1030 (m), 836 (m), 749
(m), 697 (m), 545 (s), 518 (m), 476 (m).
(1200.75): calcd. C 50.00, H 4.37, N 2.33; found C 49.71, H 4.46,
1
N 2.44. H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 1.27 (d, 12 H), Synthesis of [{(Cp*Rh)4(µ-Cl)4}(µ-1)2](PF6)4·CH2Cl2 (13): A diethyl
2.07 (s, 6 H), 2.95 (sept, JH,H ϭ 7.0 Hz, 2 H), 4.12 (m, 4 H), 4.27 ether solution (30 mL) of AgPF6 (26 mg, 0.1 mmol) was added to
(m, 4 H), 4.35 (m, 4 H), 4.49 (m, 4 H), 5.14 (d, JH,H ϭ 3.0 Hz, 4 a solution of 5 (52 mg, 0.05 mmol) in dichloromethane (30 mL),
H), 5.36 (d, JH,H ϭ 3.0 Hz, 4 H), 6.80 (m, 4 H), 8.58 (m, 4 H) ppm.
and the mixture was stirred for 12 h at room temperature. The re-
IR (KBr): ν˜ ϭ 3085 cmϪ1 (w), 3037 (w), 2961 (w), 2870 (w), 1593 sulting orange solution was filtered, the solvents evaporated to dry-
(s), 1480 (m), 1418 (m), 1111 (m), 1059 (m), 1026 (m), 890 (m), 816 ness and the red residue recrystallized from dichloromethane/di-
(m), 725 (m), 500 (m), 419 (m).
ethyl ether (1:1 v/v). The orange solid of 13 was obtained in a yield
of 27% (21 mg). C81H94Cl6F24Fe2N4P4Rh4S4 (2567.81): calcd. C
37.89, H 3.69, N 2.18; found C 38.08, H 3.34, N 2.02. 1H NMR
(400 MHz, [D6]DMSO, 25 °C): δ ϭ 1.54 (s, 60 H), 4.72 (m, 8 H),
4.76 (m, 8 H), 7.31 (m, 8 H), 8.36 (m, 8 H) ppm. IR (KBr): ν˜ ϭ
1596 cmϪ1 (s), 1482 (m), 1422 (m), 1377 (m), 1112 (m), 1062 (m),
1023 (m), 844 (s).
Synthesis of [Cp*RhCl(µ-Cl)}2(µ-2)]·CH2Cl2 (8): The procedure was
similar to that described for the preparation of 5, except that 2
(30 mg, 0.05 mmol) was used instead of 1. The orange solid of 8
was obtained in a yield of 52% (32 mg). C51H56Cl6Fe2N2Rh2S2
(1291.37): calcd. C 47.43, H 4.37, N 2.17; found C 47.6, H 4.5, N
1
2.1. H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 1.54 (s, 30 H), 4.12
(m, 4 H), 4.27 (m, 4 H), 4.35 (m, 4 H), 4.50 (m, 4 H), 6.86 (m, 4
Synthesis of [{(Cp*Ir)4(µ-Cl)4}(µ-1)2](PF6)4 (14): The procedure was
H), 8.55 (m, 4 H) ppm. IR (KBr): ν˜ ϭ 2870 cmϪ1 (w), 1636 (m), similar to that described for the preparation of 13, except that 6
1592 (s), 1478 (m), 1417 (m), 1374 (m), 1215 (m), 1165 (m), 1109 (61 mg, 0.05 mmol) was used instead of 5. The yellow solid of 14
(m), 1061 (m), 1024 (m), 890 (m), 817 (m), 725 (m), 499 (m).
was obtained in a yield of 16% (16 mg). C80H92Cl4F24Fe2Ir4N4P4S4
(2840.14): calcd. C 33.83, H 3.26, N 1.97; found C 33.44, H 3.00,
N 2.18. H NMR (400 MHz, [D6]DMSO, 25 °C): δ ϭ 1.55 (s, 60
H), 4.73 (m, 8 H), 4.77 (m, 8 H), 7.31 (m, 8 H), 8.43 (m, 8 H) ppm.
IR (KBr): ν˜ ϭ 1598 cmϪ1 (s), 1483 (m), 1458 (m), 1425 (m), 1387
(m), 1230 (m), 1140 (m), 1115 (m), 1061 (m), 1031 (m), 848 (s).
Synthesis of [{Cp*IrCl(µ-Cl)}2(µ-2)]·(CH2Cl2)1.5 (9): The procedure
was similar to that described for the preparation of 6, except that
2 (30 mg, 0.05 mmol) was used instead of 1. The yellow solid of
9 was obtained in a yield of 67% (46 mg). C51.5H57Cl3Fe2Ir2N2S2
(1370.65): calcd. C 40.90, H 3.80, N 1.85; found C 41.20, H 3.89,
1
1
N 1.72. H NMR (400 MHz, CDCl3, 25 °C): δ ϭ 1.54 (s, 30 H),
X-ray Crystallographic Study: Crystals of compound 3 or 5 were
4.14 (m, 4 H), 4.28 (m, 4 H), 4.36 (m, 4 H), 4.51 (m, 4 H), 6.82 mounted on a glass fibre and transferred to the diffractometer. The
(m, 4 H), 8.58 (m, 4 H) ppm. IR (KBr): ν˜ ϭ 3075 cmϪ1 (w), 2913 X-ray data were collected with a Rigaku AFC-5S four-circle dif-
(w), 1595 (s), 1479 (m), 1420 (m), 1377 (m), 1215 (m), 1167 (m), fractometer (3) or a Rigaku Mercury CCD diffractometer (5) using
1111 (m), 1062 (m), 1031 (m), 891 (m), 822 (m), 727 (m), 500 (m). graphite-monochromated Mo-Kα radiation. Crystal data, data col-
Eur. J. Inorg. Chem. 2002, 3197Ϫ3203
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