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1 3 4
(M = Mn) (M = Co) (M = Ru)
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1
mixture of several products. Better results were obtained when H NMR spectroscopy and high resolution ESI-mass spectrom-
a 2 : 1 mixture of [Ru(dmso)4 Cl2 ] and bimptz in ethylene glycol etry. This information suggests that the complex is the dinu-
was heated in a microwave reactor for 15 min. After addition of clear ruthenium complex [Ru2 (bimptz)(m-Cl)2 (dmso)(dms)](PF6 )2
excess NH4 PF6 , the reaction mixture was subjected to column (5), which differs from 4 in that one of the dmso ligands
chromatography (silica gel). Initially, a deep red component was has been replaced by dimethylsulfide (dms, Scheme 4). Ac-
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eluted, followed by a broad yellow band that contained the main cordingly, the mass spectrum showed two peaks correspond-
product. NMR (1 H and 13 C) and ESI-MS analyses identified the ing to the mono- and dicationic species {[Ru2 (bimptz)(m-
latter as the dinuclear complex [Ru2 (bimptz)(dmso)2 (m-Cl)2 ](PF6 )2 Cl)2 (dmso)(dms)](PF6 )}+ (m/z = 1036.9750, calc. 1036.9777)
(4), and an X-ray diffraction analysis confirmed this formulation and [Ru2 (bimptz)(m-Cl)2 (dmso)(dms)]2+ (m/z = 446.0057, calc.
(Fig. 3). 446.0068), respectively. In the 1 H NMR spectrum of 5 a new
signal for the (CH3 )2 S protons was detected, while in comparison
to the spectrum of 4 the integration for the (CH3 )2 SO protons was
reduced by half. The relatively harsh reaction conditions employed
for the preparation of 4 are possibly responsible for the partial
deoxygenation of dimethylsulfoxide, which leads to the formation
of 5 as a byproduct.
4318 | Dalton Trans., 2011, 40, 4315–4323 This journal is © The Royal Society of Chemistry 2011
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unreasonable, the structural data were examined for the presence Table 3 CVa data of the ruthenium complexes 4 and 6
of additional protons, and indeed it proved possible to locate two
“new” hydrogen atoms (H7, H7¢) within the structure (Fig. 4). Complex E 1/2 ox (DE)
In each bimptz ligand, one of the dangling N-methylimidazole [Ru2 (bimptz)(dmso)2 (m-Cl)2 ](PF6 )2 4 0.78 (68), 1.58(78)
rings is protonated and these protons are hydrogen-bonded to [Ru(Hbimptz)2 ](PF6 )4 6 0.79 (70)
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Fig. 4 Molecular structure of 6. The four PF6 - counterions and all Conclusions
hydrogen atoms except H7/H7¢ were omitted for clarity. The hydrogen
atom H7 was found from a difference Fourier map and freely refined in Here we describe the synthesis and coordination properties of
the subsequent least square cycles. Selected bond distances [Å] and angles the neutral ligand bimptz, which is accessible in three steps
[◦ ]: Ru–N1 2.035(2), Ru–N3 2.052(2), Ru–N5 2.054(2), N7–H7 0.89(4), starting from N-methylimidazole and diethoxycarbonate. Bimptz
N9¢–H7 1.79(4); N5–Ru–N1¢ 177.10(9), N3–Ru–N3¢ 178.1(2), N1–Ru–N1¢ contains a bridging phthalazine unit with four tethered imidazolyl
93.4(2), N1–Ru–N3¢ 96.18(8), N7–H7–N9¢ 174(4). rings, and it is therefore able to provide up to 6 donor sites
for the coordination of metal ions. The potential of bimptz for
Further evidence for the presence of two additional protons in 6 the synthesis of dinuclear metal complexes was demonstrated in
is provided by high-resolution ESI-MS analysis. For an acetonitrile reactions with MnCl2 ·4H2 O, CoCl2 ·6H2 O and [Ru(dmso)4 Cl2 ],
solution of the complex, signals were observed for the complex from which the corresponding dimetallic complexes 1, 3 and 4
cation [Ru(Hbimptz)2 ]4+ (m/z = 265.0968; calc. 265.0965), and could be obtained. The molecular structures of the latter are
for its PF6 - salt {[Ru(Hbimptz)2 ](PF6 )2 }2+ . Peaks corresponding similar and contain two metal ions in a more or less distorted
to the trication [Ru(Hbimptz)(bimptz)]3+ (m/z = 353.1265; calc. octahedral ligand environment. In all structures the two metal
353.1263) and its PF6 - adduct {[Ru(Hbimptz)(bimptz)](PF6 )}2+ ions are bridged by the phthalazine moiety and two m-chloro
provide evidence that deprotonation occurs to a certain degree ligands. Diamond-like M2 (m-Cl2 ) units are found in the cobalt
in solution. and ruthenium complexes 3 and 4, while the M–Cl bond lengths
In 6 each of the two bimptz ligands contributes three N- within the corresponding core of the manganese complex 1 reflect
donor sites to the slightly distorted octahedral coordination of a significant bond alternation. The electrochemical properties of
the Ru(II) center, leaving the other three nitrogen donors available the two ruthenium complexes were investigated by means of cyclic
for further reactivity. Complex 6 is C 2 -symmetric and contains voltammetry, which shows two reversible one electron oxidations
a crystallographic axis of symmetry that passes through the for 4 and one reversible oxidation wave for 6. Further work
ruthenium center and bisects the angle spanned by N1, Ru and will focus on the synthesis of chlorine free, dinuclear complexes
N1¢. As mentioned above, two of the dangling imidazolyl rings are of bimptz and on investigations of the ability of 6 to act as
protonated and are involved in hydrogen bonds to the nitrogen a precursor for the preparation of heteronuclear metal comp-
atoms of additional imidazolyl rings. lexes.
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Experimental section (m), 1579 (m), 1546 (m), 1523 (m), 1490 (vs), 1458 (m), 1412 (s),
1396 (s), 1361 (s), 1284 (s), 1271 (s), 1244 (m), 1177 (w), 1136 (s),
General considerations 1082 (w), 1047 (w), 936 (w), 923 (w), 872 (m), 859 (s), 810 (m), 763
(s), 750 (vs), 717 (m), 695 (s), 678 (m), 662 (s), 650 (m), 586 (m), 550
Bis(N-methylimidazol-2-yl)methane, Im¢CH2 Im¢, was synthesized
(s), 525 (w), 490 (w), 441 (w). UV-Vis (CH3 CN): l max /nm, (loge) =
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4320 | Dalton Trans., 2011, 40, 4315–4323 This journal is © The Royal Society of Chemistry 2011
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0.248 g (0.24 mmol, 58%). Anal. calc. for C28 H38 Cl2 Co2 F12 N10 O4 P2 , Preparation of [Ru2 (bimptz)(dmso)(dms)(l-Cl)2 ][PF6 ]2 (5)
[Co2 (bimptz)(CH3 OH)2 Cl2 ](PF6 )2 ·2H2 O: C 31.81, H 3.62, N 13.25,
Cl 6.71. Found: C 31.38, H 3.57, N 13.23, Cl 6.72%. The evaporated dark red second fraction obtained from the
IR: n/cm-1 = 3634 (m), 3163 (m), 2966 (m), 1616 (m), purification of 4 was worked up analogously as described for 4
1569 (w), 1539 (m), 1516 (s), 1464 (m), 1414 (s), 1352 (m), yielding 5 as dark red crystalline solid. Yield: 0.053 g (45 mmol,
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1288 (m), 1177 (m), 1169 (m), 1140 (m), 1090 (m), 1038 21%).
(w), 960 (m), 842 (vs), 760 (s), 740 (m), 719 (m), 675 (w),
1
H-NMR (CD3 CN): d/ppm = 9.03 (m, 2H, CH ptz ), 8.38
660 (m), 635 (m), 557 (s), 447 (m). MS (ESI+ (CH3 CN), (m, 2H, CH ptz ), 7.09 (d, 2H, 3 J(H,H) = 1.4 Hz, CH im ), 7.03
m/z): 811.0 (100%, {[Co2 (bimptz)Cl2 ](PF6 )}+ ), 353.5 (40%, (d, 2H, 3 J(H,H) = 1.4 Hz, CH im ), 7.00 (d, 2H, 3 J(H,H) =
[Co2 (bimptz)Cl2 (CH3 CN)]2+ ), 333.0 (45%, [Co2 (bimptz)Cl2 )]2+ ). 1.4 Hz, CH im ), 6.98 (d, 2H, 3 J(H,H) = 1.4 Hz, CH im ) 6.93 (s,
HRMS (ESI+ (CH3 CN), m/z): Calc. for C26 H26 N10 35 Cl2 59 Co2 F6 P1 1H, (Ptz)(Im)2 CH), 6.89 (s, 1H, (Ptz)(Im)2 CH), 3.93 (s, 12H,
({[Co2 (bimptz)Cl2 ]}(PF6 )+ ): 811.0019. Found: 811.0007. Calc. NCH 3 ), 3.38 (s, 6H, H dmso ), 2.37 (s, 6H, H dms ). IR: n/cm-1 =
for C28 H29 N11 35 Cl2 59 Co2 ([Co2 (bimptz)Cl2 (CH3 CN)]2+ ): 707.0648. 3147 (w), 2959 (m), 2920 (m), 2851 (m), 1624 (br), 1541 (m),
Found: 707.0630. 1519 (m), 1464 (w), 1427 (m), 1348 (w), 1286 (m), 1261 (w),
1236 (w), 1176 (w), 1088 (m), 1060 (w), 1018 (m), 982 (m),
912 (w), 840 (vs), 756 (m), 715 (w), 688 (w), 661 (w), 578
Preparation of [Ru2 (bimptz)(dmso)2 (l-Cl)2 ](PF6 )2 (4) (w), 557 (s), 427 (w). UV-Vis (CH3 CN): l max /nm, (loge) =
Bimptz (0.100 g, 0.21 mmol) and [Ru(dmso)4 Cl2 ] (202.5 mg, 503 (sh), 416 (3.71), 292 (3.85), 234 (4.67), 209 (4.53). HRMS
0.41 mmol), each dissolved in 12 mL of ethylene glycol, were (ESI+ (CH3 CN), m/z): Calc. for C30 H38 O1 N10 35 Cl2 F6 P1 102 Ru2 32 S2
mixed to yield an orange-colored solution, which was degassed by ({[Ru2 (bimptz)(dmso)(dms)Cl2 ](PF6 )}+ ): 1036.9777. Found:
evacuation and purging with argon three times. After refluxing 1036.9750. Calc. for C30 H38 O1 N10 35 Cl2 102 Ru2 32 S2 ([Ru2 (bimptz)-
the reaction mixture in a microwave reactor under argon for (dmso)(dms)Cl2 ]2+ ): 446.0068. Found: 446.0057.
15 min, a solution of NH4 PF6 (1.36 g) in 10 mL of water was
added to the still hot brown-red solution. Cooling to 0 ◦ C and Preparation of [Ru(Hbimptz)2 ](PF6 )4 (6)
filtering yielded a brown crude product, which was washed with
cold water and THF. The crude product was purified by column Bimptz (0.200 g, 0.42 mmol) and [Ru(dmso)4 Cl2 ] (0.101 g,
chromatography on silica and the column eluted with acetonitrile– 0.21 mmol), each dissolved in 25 mL ethylene glycol were mixed
aqueous saturated KPF6 (9 : 1). The first pale red fraction was and heated to 100 ◦ C in an oil bath under argon. After 10 min at
rejected, the following narrow dark red and broad yellow bands this temperature the red solution was refluxed for an additional
were collected. 4 was contained in the third (yellow) fraction 5 h. Solid NH4 PF6 (1.36 g) was then added to the still hot
(along with KPF6 ), which was evaporated to dryness using a reaction mixture. After cooling to room temperature 6 was isolated
rotovap. The residue was stirred in approximately 40 mL of as a fine microcrystalline dark purple solid, which was washed
water in order to dissolve the KPF6 salt. After filtration a dark subsequently with cold water and ether and dried in vacuo. Yield:
brown solid of crude 4 was obtained, which was washed with a 0.155 g (0.11 mmol, 55%). Anal. calc. for C52 H54 N20 F24 P4 Ru,
minimum amount of cold water, followed by tetrahydrofuran and [Ru(Hbimptz)2 ](PF6 )4 : C 38.08, H 3.32, N 17.08. Found C 37.68,
ether. 4 was dried in vacuo and recrystallized by slow diffusion of H 3.52, N 16.58%.
tetrahydrofuran into a solution of 4 in acetonitrile. Yield: 0.122 g 1
H-NMR (CD3 CN): d/ppm = 8.96 (d, 1H, 3 J(H,H) = 8.6 Hz,
(0.1 mmol, 48%). Anal. calc. for C30 H38 Cl2 F12 N10 O2 P2 Ru2 S2 , CH ptz ), 8.24 (m, 1H, CH ptz ), 7.93 (m, 1H, CH ptz ), 7.36 (d, 1H,
3
[Ru2 (bimptz)(dmso)2 Cl2 ](PF6 )2 : C 30.08, H 3.20, N 11.69, Cl J(H,H) = 8.3 Hz, CH ptz ), 7.17 (d, 1H, 3 J(H,H) = 1.2 Hz, CH im ),
5.92, S 5.35. Found: C 30.32, H 3.33, N 11.23, Cl 6.46, 7.08 (d, 1H, 3 J(H,H) = 1.4 Hz, CH im ), 7.03 (d, 1H, 3 J(H,H) =
S 4.52%. 1.4 Hz, CH im ), 6.88 (s, 1H, (Ptz)(Im)2 CH), 6.66 (d, 1H, 3 J(H,H) =
1
H-NMR (CD3 CN): d/ppm = 9.10 (m, 2H, CH ptz ), 8.47 (m, 1.9 Hz, CH im ), 6.64 (s, 1H, (Ptz)(Im)2 CH), 6.36 (d, 1H, 3 J(H,H) =
2H, CH ptz ), 7.08 (d, 4H, 3 J(H,H) = 1.6 Hz, CH im ), 7.01 (d, 4H, 1.4 Hz, CH im ), 6.27 (d, 1H, 3 J(H,H) = 1.3 Hz, CH im ), 6.07 (d, 1H,
3 3
J(H,H) = 1.6 Hz, CH im ), 6.95 (s, 2H, (Ptz)(Im)2 CH), 3.93 (s, J(H,H) = 1.4 Hz, CH im ), 5.30 (d, 1H, 3 J(H,H) = 1.9 Hz, CH im ),
12H, NCH 3 ), 3.37 (s, 12H, H dmso ). 13 C-NMR (CD3 CN): d/ppm = 4.15 (s, 3H, NCH 3 ), 4.03 (s, 3H, NCH 3 ), 3.65 (s, 3H, NCH 3 ), 3.47
164.5, 140.4, 137.6, 132.5, 127.4, 125.9, 124.5, 47.2, 35.7, 35.5. (s, 3H, NCH 3 ). 13 C-NMR (CD3 CN): d/ppm = 159.5, 155.3, 142.1,
IR: n/cm-1 = 3144 (m), 3021 (w), 2968 (m), 2923 (m), 2851 (w), 141.5, 140.1, 140.0, 136.1, 134.0, 130.7, 129.8, 128.1, 126.9, 126.6,
1628 (m, br), 1545 (m), 1521 (s), 1448 (m), 1424 (m), 1412 (m), 125.0, 124.7, 124.3, 124.1, 123.8, 123.7, 119.4, 39.0, 35.9, 35.2,
1350 (m), 1320 (w), 1287 (m), 1177 (m), 1150 (w), 1088 (s), 1018 35.1, 34.9, 34.4. IR: n/cm-1 = 3163 (m), 2956 (m), 2927 (m), 2869
(s), 982 (w), 965 (w), 910 (w), 839 (vs), 758 (m), 742 (m), 715 (w), 2854 (w), 1610 (m), 1576 (w), 1543 (s), 1521 (s), 1500 (m), 1460
(m), 687 (w), 668 (w), 662 (w), 638 (w), 577 (m), 558 (s), 439 (m), 1441 (w), 1427 (m), 1358 (w), 1323 (w), 1288 (s), 1238 (w),
(m), 426 (m). UV-Vis (CH3 CN): l max /nm, (loge) = 458 (sh, 3.61), 1170 (m), 1148 (m), 1092 (m), 1051 (w), 1041 (w), 1016 (w), 957
396 (3.93), 286 (4.05), 236 (4.79). MS (ESI+ (CH3 CN), m/z): (w), 834 (vs), 756 (s), 715 (m), 704 (w), 694 (w), 669 (w), 663(w),
1052.7 (15%, {[Ru2 (bimptz)(dmso)2 Cl2 ](PF6 )}+ ), 453.9 (100%, 640 (w), 621 (w), 601 (w), 557 (s), 538 (w). UV-Vis (CH3 CN):
[Ru2 (bimptz)(dmso)2 Cl2 ]2+ ). HRMS (ESI+ (CH3 CN), m/z): Calc. l max /nm, (loge) = 515 (4.21), 421 (4.00), 293 (4.15), 224 (5.02). MS
for C30 H38 O2 N10 35 Cl2 F6 P1 102 Ru2 32 S2 {([Ru2 (bimptz)(dmso)2 ]- (ESI+ (CH3 CN), m/z): 674.9 (10%, {[Ru(Hbimptz)2 ](PF6 )2 }2+ ),
Cl2 (PF6 )}+ ): 1052.9721. Found: 1052.9733. Calc. for 601.9 (15%, {[Ru2 (Hbimptz)(bimptz)](PF6 )}2+ ), 353.3 (100%,
C30 H38 O2 N10 35 Cl2 102 Ru2 32 S2 ([Ru2 (bimptz)(dmso)2 Cl2 ]2+ ): 454.0037. [Ru2 (Hbimptz)(bimptz)]3+ ), 265.2 (85%, [Ru2 (Hbimptz)2 ]4+ ).
Found: 454.0053. HRMS (ESI+ (CH3 CN), m/z): Calc. for C52 H54 F12 N20 P2 102 Ru
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Empirical formula C28 H34 Cl4 Mn2 N10 O2 C28 H34 Cl2 Co2 F12 N10 O2 P2 C38 H52 Cl2 F12 N12 O3 P2 Ru2 S2 C52 H54 F24 N20 P4 Ru
Formula weight 794.33 1021.35 1352.02 1640.10
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({[Ru(Hbimptz)2 ](PF6 )2 }2+ ): 675.1584. Found: 675.1589. Calc. for tetrahydrofuran into a diluted solution of 4 in acetonitrile. 6: slow
C52 H54 N20 102 Ru ([Ru2 (Hbimptz)2 ]4+ ): 265.0965. Found: 265.0968. evaporation of the solvent from an acetone–methanol solution of
6. Crystallographic data for the structures 1, 3, 4 and 6 have been
deposited with the Cambridge Crystallographic Data Centre as
Crystal structure determinations† supplementary publication no. 765497 (1), 765495 (3), 765496 (4),
All data were collected on a Stoe IPDS-2T diffractometer using 765494 (6).†
MoKa radiation, l = 0.71073 Å. In all cases, the structures were
solved by direct methods (SHELXS-97)19 and refined versus F 2 Acknowledgements
(SHELXL-97)20 with anisotropic temperature factors for all non-
hydrogen atoms (Table 4). In 1 one of the two co-crystallized This work was funded by the Deutsche Forschungsgemeinschaft
methanol molecules could not be modeled satisfactory and was as well as the Helios Solar Energy Research Center, which is
excluded using the program SQUEEZE (Platon)21 In the crystal supported by the Director, Office of Science, Office of Basic
structure of 3 there is a region of disordered solvent molecules Energy Sciences of the U.S. Department of Energy under Contract
which could not be modeled successfully (trial modeling attempts No. DE-AC02-05CH11231. S.R thanks the DAAD (German
indicated a mixture of methanol and diethyl ether). The program Academic Exchange Service) for a postdoctoral fellowship.
SQUEEZE (Platon)21 was used to remove the contribution of these
diffusely scattering species from the structure factor calculations.
The program calculated a solvent accessible region of 2404 Å3 References
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4322 | Dalton Trans., 2011, 40, 4315–4323 This journal is © The Royal Society of Chemistry 2011
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