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Microwave methods for the synthesis of paddlewheel diruthenium compounds with N,N-donor ligands
Santiago Herrero, Reyes Jim nez-Aparicio,* Josena Perles, Jos L. Priego, Susana Saguar and e e Francisco A. Urbanos
Downloaded by University of Alberta on 27 July 2011 Published on 09 June 2011 on http://pubs.rsc.org | doi:10.1039/C0GC00800A

Received 11th November 2010, Accepted 11th April 2011 DOI: 10.1039/c0gc00800a Microwave irradiation can lead to easy and fast synthesis methods in the obtention of paddlewheel diruthenium complexes with N,N-donor ligands. Microwave assisted substitution of acetate groups on [Ru2 Cl(O2 CMe)4 ] by three different types of N,N-donor ligands gives rise to [Ru2 (DPhT)4 ] (1), (DPhT- = 1,3-diphenyltriazenide); [Ru2 (DFPhT)4 ] (2), (DFPhT- = 1,3bis(p-uorophenyl)triazenide); [Ru2 Cl(DPhF)4 ] (3), (DPhF- = 1,3-diphenylformamidinate); [Ru2 Cl(DAniF)4 ] (4), (DAniF- = 1,3-bis(p-methoxyphenyl)formamidinate); and [Ru2 Cl2 (hpp)4 ] (5), (hpp- = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate). In addition, the selective replacement of the acetate group on [Ru2 Cl(DPhF)3 (O2 CMe)] by [1,3,5-(O2 C)3 C6 H3 ]3- under microwave irradiation produces {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O, (6). The experimental conditions have been optimised in every case to obtain better yields and more environmentally friendly reaction conditions than the ones reported by other conventional methods of synthesis.

Introduction
Bridging N,N-donor ligands such as triazenide, formamidinate or guanidinate are widely used in the formation of dimetallic complexes containing a variety of metalmetal bond orders.1 The p-bond in these ligands allows the delocalization of the negative charge across the NXN (X = C, N) backbone leading to stable complexes.1 Furthermore, by varying the electron donor ability of the N-substituents, the electron density of the dimetallic core can be modied without an important change in the fundamental geometry of the complex. Many examples containing a M2 n+ (n = 4 and 6) paddlewheel core have been described, and mixed valence compounds with M2 5+ units are also known for several metals.1 In ruthenium chemistry, complexes containing Ru2 5+ units are especially stable compared with the reduced Ru2 4+ or oxidized Ru2 6+ core.1,2 Additionally, the study of the magnetic properties of these ruthenium complexes is very attractive due to their singularity.3,4 Recently, the use of diruthenium building-blocks to construct molecular wires has renewed the interest in these types of complexes for their potential applications in nanoscience and nanotechnology.5

Departamento de Qumica Inorg nica, Facultad de Ciencias Qumicas, a Universidad Complutense de Madrid, Ciudad Universitaria, 28040, Madrid, Spain. E-mail: reyesja@quim.ucm.es; Fax: (+) 34 1 3944352; Tel: (+) 34 1 3944334; Web: http://www.ucm.es/info/inorg1/qcmm/qcmm.htm Electronic supplementary information (ESI) available. CCDC reference numbers 814431814434. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0gc00800a

Unfortunately, the preparation of paddlewheel diruthenium complexes with N,N-donor ligands usually requires drastic reaction conditions such as fused ligands or high temperatures.1 These difculties have hindered the development of the chemistry of these complexes, especially in the case of triazenido derivatives. Thus, new and more environmentally friendly experimental procedures are convenient for the preparation of these compounds. From this point of view, microwave activation,6 which has been extensively used in organic reactions,7 emerges as an alternative in coordination chemistry, as it can improve the reaction conditions, selectivity, yield or purity of the nal compounds. In a previous communication we reported the successful application of microwave energy in the obtention of tetrakis(diaryltriazenido)diruthenium complexes.8 Previously, Powell and Johnson9 had also observed that microwave activation was useful to prepare dimolybdenum compounds. In this work, we present new methods to synthesise diruthenium complexes in order to prove the general validity of this approach in the synthesis of paddlewheel diruthenium compounds with N,N-donor ligands. We have extended the use of microwave irradiation, in particular, to the synthesis of complexes with 1,3diarylformamidinate (DArF- ) and 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate (hpp- ) (Fig. 1).

Results and discussion

The main concern of the chemist when designing a synthetic process is usually the easy and rapid obtention of the desired Green Chem., 2011, 13, 18851890 | 1885

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Fig. 1 N,N-donor ligands 1,3-diaryltriazenide, DArT- (a), 1,3-diarylformamidinate, DArF- (b) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2a]pyrimidinate, hpp- (c).

Downloaded by University of Alberta on 27 July 2011 Published on 09 June 2011 on http://pubs.rsc.org | doi:10.1039/C0GC00800A

product in a good yield. One-step reactions in which the nal compound appears as a single solid phase are especially appealing, as they do not require troublesome separation and purication steps. In a green chemistry approach, however, other issues must be contemplated, namely the reduction of waste, the atom economy and the improvement of the procedure efciency. Following these motivations, our group has revised the synthetic methods used so far to obtain paddlewheel diruthenium compounds with N,N-donor ligands, trying to nd better reaction pathways (Table 1). As a result, we have used closed vessel microwave methods for the synthesis of complexes [Ru2 (DPhT)4 ] (1), (DPhT- = 1,3diphenyltriazenide); [Ru2 (DFPhT)4 ] (2), (DFPhT- = 1,3-bis(puorophenyl)triazenide); [Ru2 Cl(DPhF)4 ] (3), (DPhF- = 1,3diphenylformamidinate); [Ru2 Cl(DAniF)4 ] (4), (DAniF- = 1,3(5), bis(p-methoxyphenyl)formamidinate), [Ru2 Cl2 (hpp)4 ] (hpp- = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) and {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O (6), testing several experimental parameters to attain better reaction conditions. Tetrakis(1,3-diaryltriazenido)diruthenium complexes (1 and 2) In the synthesis of tetrakis(1,3-diphenyltriazenido)diruthenium(II), compound 1; and tetrakis[1,3-bis(p-uorophenyl)triazenido]diruthenium(II), compound 2, several reaction conditions were tested to maximise the yield and minimise both the waste generation and energy consumption.8 Three solvents were used, namely 2-methoxyethanol, THF and ethanol, and it was proved that the solvent was decisive in the outcome of the reaction. With 2-methoxyethanol, the reaction did not take place, whereas THF and ethanol promoted the formation of tetrakis(diaryltriazenido)diruthenium complexes. However, reactions carried out with THF gave rise to a

mixture of chloridotetrakis(diaryltriazenido)diruthenium(II,III) and tetrakis(diaryltriazenido)diruthenium(II) compounds. Total selectivity of the synthetic procedure was achieved when the chosen solvent was ethanol. The effect of the reaction time was also tested, and the results indicated that it has inuence both in the selectivity and the yield of the synthesis. Reaction times shorter than 2 h gave rise to a mixture of chloridotetrakis(diaryltriazenido)diruthenium(II,III) and tetrakis(diaryltriazenido)diruthenium(II), suggesting that the substitution of the ligands is followed by the reduction of the species. With a reaction time of 2 h, the achieved yield is 78%, and a better yield of ~90% can be obtained in 8 h. The reaction temperature was also found to have an inuence on the selectivity of the procedure, as temperatures lower than 130 C yielded a mixture of the above mentioned Ru2 4+ and Ru2 5+ derivatives. Following the atom economy principle, two reactants initially included in the reaction mixture were attempted to be removed, as they did not take part in the nal product. The removal of LiCl was found to have no effect on the nal outcome, while Et3 N proved to be indispensable for the deprotonation of the triazene. Finally, dilution and cooling time of the vessel were found to affect only the crystallinity of the obtained product.

Chloridotetrakis(diarylformamidinato)diruthenium complexes (3 and 4) Complexes 3 and 4 have been obtained from [Ru2 Cl(O2 CMe)4 ] and formamidine by a one-step microwave assisted method. The preparation of tetrakis(formamidinato)diruthenium compounds had been previously described10 using argon atmosphere, a great excess of formamidine or high temperature for long periods of time. In particular, for [Ru2 Cl(DPhF)4 ], the reaction mixture contained [Ru2 Cl(O2 CMe)4 ] and HDPhF with a 1 : 147 dimetal : formamidine ratio and was heated at 150 C during 3 h to maintain the ligand fused.10a A second way of obtention of this type of complexes involved reuxing THF as a solvent and an amine to facilitate the deprotonation of the formamidine.11 However, in the case of 1,3-diphenylformamidine this latter method leads to other partially substituted compounds in addition to tetrakis(formamidinato)diruthenium(II,III), which had to be separated from the reaction mixture, with a resulting yield lower than 16%.12

Table 1 Comparison of the experimental conditions for the preparation of complexes 15 by microwave and conventional methods Reaction time/h 8 18 8 1 3 2 48 0.25 10.5 2 Reaction temperature/ C 130 RT 130 130 150 130 110 130 150 -78/RT Reaction atmosphere air Ar air air Ar air air air Ar air

Compound [Ru2 (DPhT)4 ] (1) [Ru2 (DFPhT)4 ] (2) [Ru2 Cl(DPhF)4 ] (3) [Ru2 Cl(DAniF)4 ] (4) [Ru2 Cl2 (hpp)4 ] (5)

Method MW Conventional15 MW MW Conventional10a MW Conventional10c MW Conventional13a Conventional13b

Solvents used EtOH Et2 O, MeOH, toluene EtOH THF molten HDPhF, CH2 Cl2 , hexane, pentane THF, MeOH, Et2 O CH2 Cl2 , toluene, hexane EtOH, H2 O, Et2 O molten Hhpp, MeOH, CH2 Cl2 , hexane THF, CH2 Cl2 , Et2 O

M2 : L 1:6 1:4 1:6 1:6 1 : 147 1:8 1 : 10.75 1 : 12 1 : 17 1:4

Steps 1 5 1 1 5 1 4 1 6 7

Yield/% 90 44 92 95 ~100 91 84 98 40 82.7

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We have obtained [Ru2 Cl(DPhF)4 ] by suspending [Ru2 Cl(O2 CMe)4 ], HDPhF, LiCl and Et3 N in THF and heating the reaction mixture at 130 C during 1 h in a microwave oven. The desired compound, 3, (Fig. 2b) was obtained in excellent yield (95%). It is a remarkable fact that the selectivity of this reaction method towards the tetrakis(1,3diphenylformamidinato)diruthenium(II,III) species is total even with reaction conditions that could favour the formation of partially substituted species.

Downloaded by University of Alberta on 27 July 2011 Published on 09 June 2011 on http://pubs.rsc.org | doi:10.1039/C0GC00800A

Fig. 2 Dimeric units of [Ru2 (DArT)4 ] (a), [Ru2 Cl(DArF)4 ] (b) and [Ru2 Cl2 (hpp)4 ] (c).

Several experimental conditions were tested in the optimisation of the synthesis of 3. Different dimetal : ligand ratios were tried, and regardless of the ratio employed (even with ratios as low as 1 : 1) only tetrakis(1,3-diphenylformamidinato)diruthenium(II,III) was isolated. With ratios under 1 : 6, the yield decreases and the solid obtained is a mixture of the initial [Ru2 Cl(O2 CMe)4 ] and the product [Ru2 Cl(DPhF)4 ], and we have not detected the presence of mono-, bis- or tris(1,3-diphenylformamidinato)diruthenium(II,III) compounds. Longer reaction times than 1 h do not increase the yield of the product. Nevertheless, it was found that shorter ones signicantly reduce the yield, giving rise to a mixture of the desired product and the diruthenium reagent. For instance, heating the reaction mixture at 130 C during 15 min, the ltered solid consists of [Ru2 Cl(DPhF)4 ] and [Ru2 Cl(O2 CMe)4 ] in a 3 : 1 ratio. We observed that temperatures lower than 130 C do not allow the reaction to proceed to the end, yielding again a mixture of [Ru2 Cl(O2 CMe)4 ] and [Ru2 Cl(DPhF)4 ]. Regarding the atom economy principle, two reactions were attempted in the optimised conditions with the removal of LiCl and Et3 N, respectively. It was found that both substances are needed for the formation of tetrakis(1,3diphenylformamidinato)diruthenium(II,III). As also happened in the synthesis of tetrakis(diaryltriazenido)diruthenium species, dilution and cooling time affect only the crystallinity of the solid and do not have any effect on the yield or purity of the product. Dichloridotetrakis(guanidinato)diruthenium complex (5) Two procedures had been described in the literature for the synthesis of [Ru2 Cl2 (hpp)4 ]. In one of them13a the synthetic conditions involved an argon atmosphere and a heating temperature of 150 C for a 10.5 h period. Afterwards, the excess of Hhpp needed to be sublimated and the compound puried on an alumina column, attaining a yield of 40%. The other method13b improved the purity and yield aspects, but also involved many reaction steps, some of them quite tedious, a reagent as dangerThis journal is The Royal Society of Chemistry 2011

ous and difcult to handle as BuLi, and a highly contaminating halogenated solvent such as dichloromethane. In the microwave assisted synthesis of [Ru2 Cl2 (hpp)4 ], the reaction time has been greatly reduced and the yield and atom economy aspects have also been improved. A mixture of [Ru2 Cl(O2 CMe)4 ], Hhpp and LiCl in a small amount of EtOH is heated at 130 C, and with a reaction time as short as 15 min the desired product is formed with a 98% yield. In the optimisation process of this synthetic method, the tested parameters were the dimetal : ligand ratio, time, temperature, solvent used and need for auxiliary reagents. The reaction with THF as a solvent was not successful. Using EtOH, however, the compound was isolated as a single phase of microcrystals. The amount of ligand was found to be a key factor in this reaction. With an initial dimetal : ligand ratio of 1 : 6, the obtained yield of 70% could not be improved even with longer reaction times and higher temperatures. Actually, more drastic conditions regarding temperature or time were found to cause a slight decrease in the reaction yield. Nevertheless, when the excess of ligand is increased and the ratio employed is 1 : 12, the product is formed quantitatively. Concerning the use of auxiliary reagents, it is interesting to note that there is no need to include a deprotonating agent in this process, as opposed to what happened in the synthesis of tetrakis(diaryltriazenido)- or tetrakis (diarylformamidinato)diruthenium compounds. The removal of the amine can probably be done because the excess of guanidine acts as a deprotonating agent. Finally, it was also found that dilution and cooling time do not affect the yield or selectivity of the process. {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O complex (6) The same approach has also been used for the exchange of the carboxylate ligand in the acetatochloridotris(1,3compound, diphenylformamidinato)diruthenium(II,III) [Ru2 Cl(DPhF)3 (O2 CMe)]. The reaction under microwave radiation between [Ru2 Cl(DPhF)3 (O2 CMe)] and trimesic acid in methanol produces complex 6 in good yield. The synthesis of {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }H2 O had been described starting from the same reactants in reuxing methanol.14 In the microwave synthesis, the reaction time has been shortened from 4 h to 45 min and one reagent (LiCl) has been eliminated with a slightly better yield. In connection with the selectivity of the method, the microwave assisted reaction with a dimetal : trimesic acid ratio as low as half the stoichiometric one (1.5 : 1 instead of 3 : 1) does not lead to a mixture of compounds but to a single phase of the {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O compound with 44% yield. This behaviour can be explained by considering the augment in the reactivity of the remaining carboxylate groups due to an increase of their acidity upon successive coordination of the diruthenium fragments. The improvement of the reaction conditions in this case is noteworthy, and furthermore, this procedure proves also the possibility of applying microwave methods to other syntheses involving paddlewheel complexes, such as the selective activation of a particular ligand. Green Chem., 2011, 13, 18851890 | 1887

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Inuence of the microwave activation in the oxidation state of the diruthenium unit In the reaction of [Ru2 Cl(O2 CMe)4 ] with N,N-donor ligands we have observed several redox processes. Thus, with diaryltriazenide ligands, the initial Ru2 5+ unit is reduced yielding Ru2 4+ compounds. The relatively low basic character of these ligands and the use of ethanol as a reaction solvent could favour the reduction process. The change of ethanol by THF leads to a mixture of Ru2 4+ and Ru2 5+ complexes8 suggesting the complementary inuence of the solvent. However, in the reaction with diarylformamidine in THF, no redox process was observed and only Ru2 5+ complexes were isolated. This could be explained by the increase of the donor character in the ligand which causes an increment of the electronic density of the diruthenium core and leads to a stabilization of Ru2 5+ units. In the reaction with Hhpp, the stronger basic character of hpp- favours the oxidation of the dimetallic core to give the corresponding Ru2 6+ unit. A similar oxidation process using the hpp- ligand occurs when the complex is synthesised by conventional methods.13

Downloaded by University of Alberta on 27 July 2011 Published on 09 June 2011 on http://pubs.rsc.org | doi:10.1039/C0GC00800A

conditions: 0.25 mmol (0.12 g) of [Ru2 Cl(O2 CMe)4 ], 1.5 mmol of triazene (0.25 g of 1,3-diphenyltriazene or 0.35 g for 1,3-bis(puorophenyl)triazene), 0.25 mL of triethylamine and 10 mL of absolute ethanol were placed into a 85 mL TFM Teon vessel with a magnetic stirrer. The vessel was sealed with a lid equipped with a temperature sensor, and placed in the microwave oven. The reaction mixture was heated for 8 h at 130 C. The reaction mixture was left to cool afterwards, giving rise to the compound as a single phase of deep purple crystals with a 90% yield. The crystals were ltered off and washed with 10 mL of cold ethanol. Complexes 1 and 2 were characterised19 by elemental analysis, IR spectroscopy and single X-ray diffraction methods (Fig. S1 S3, ESI). The samples were also analysed by powder X-ray diffraction to ensure the purity of the bulk material. Synthesis of [Ru2 Cl(DPhF)4 ] (3) Into a 85 mL TFM Teon vessel with a magnetic stirrer were placed 0.5 mmol (0.25 g) of [Ru2 Cl(O2 CMe)4 ], 3 mmol of HDPhF (0.62 g), 0.15 g of lithium chloride, 0.5 mL of triethylamine and 8 mL of THF. The vessel was sealed with a lid equipped with a temperature sensor, and placed in the microwave oven. The reaction mixture was heated for 1 h at 130 C and left to cool afterwards. Compound 3 was obtained as a single phase of blackgreen crystals with a 95% yield. The crystals were ltered off and washed with 10 mL of cold THF. Compound 3 was characterised20 by elemental analyses, IR spectra, and single crystal X-ray diffraction (Fig. S4, ESI). The sample was also analysed by powder X-ray diffraction to ensure the purity of the bulk material. Synthesis of [Ru2 Cl(DAniF)4 ] (4) In the synthesis of compound 4, the reaction conditions applied were similar to the ones used for compound 3. In this case, 0.5 mmol (0.25 g) of [Ru2 Cl(O2 CMe)4 ], 4 mmol HDAniF (1.03 g), 0.15 g of lithium chloride, 0.5 mL triethylamine and 8 mL of THF were added to a 85 mL TFM Teon vessel equipped with a temperature sensor and a magnetic stirrer. The vessel was sealed and placed in the microwave oven, where the reaction mixture was heated for 2 h at 130 C and left to cool afterwards. The compound was separated from the mixture by ltration and washed with cold methanol and diethyl ether. It was obtained as a single phase of deep purple crystals with a 91% yield. Compound 4 was characterised21 by elemental analyses, IR spectra, and single crystal X-ray diffraction (Fig. S5, ESI). The sample was also analysed by powder X-ray diffraction to ensure the purity of the bulk material. Synthesis of [Ru2 Cl2 (hpp)4 ] (5) The optimised reaction conditions for the obtention of [Ru2 Cl2 (hpp)4 ] were the following: an 85 mL TFM Teon vessel equipped with a temperature sensor and a magnetic stirrer was charged with 0.5 mmol (0.25 g) of [Ru2 Cl(O2 CMe)4 ], 6 mmol of Hhpp (0.84 g), 0.15 g of lithium chloride and 8 mL of ethanol. It was sealed and heated in a microwave oven for 15 min at 130 C and cooled afterwards. The solid was separated by ltration from the reaction mixture and washed rst with 5 mL of cold This journal is The Royal Society of Chemistry 2011

Experimental
Microwave reactions were carried out in a ETHOS ONE microwave oven using TFM Teon vessels equipped with temperature sensor and pressure control. FT-IR spectra were recorded in a Perkin Elmer Spectrum 100 with an universal ATR accessory with a spectral range of 4000650 cm-1 . Powder X-ray diffractograms were made in a Siemens D5000 diffractometer. Elemental analyses were done by the Microanalytical Service of the Complutense University of Madrid. Reactants and solvents were used as received. [Ru2 Cl(DPhF)3 (O2 CMe)], [Ru2 Cl(O2 CMe)4 ] and HDAniF were prepared according to published general procedures.12,16,17 X-ray data collection and structure renement Data collection for compounds 14 were carried out at room temperature on a Bruker SMART CCD diffractometer equipped with a normal focus, 2.4 kW sealed-tube X-ray source (Mo Ka radiation = 0.71073 A). The data were collected over a hemisphere of the reciprocal space by combination of three exposure sets. The rst 50 frames were recollected at the end of the data collection to monitor crystal decay. Unit-cell dimensions were determined by a least-squares t of all reections collected. All non-hydrogen atoms were rened anisotropically, and some geometrical restraints were applied for phenyl rings in 1 and 1THF. All hydrogen atoms were included in their calculated positions and rened riding on the respective carbon atoms. Calculations were carried out using the SMART program for data collection and data reduction, and SHELXS18 for solution and renement. CCDC numbers for these compounds are 814431, 814432, 766373, 814433 and 814434 and supplementary crystallographic data for this paper can be found in the ESI. Synthesis of [Ru2 (DPhT)4 ] (1) and [Ru2 (DFPhT)4 ] (2) Complexes 1 and 2 have been prepared as described in a previous communication.8 The best yield was obtained with the following
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water and 5 mL of cold ethanol and afterwards with 5 mL of diethylether to obtain compound 5 as a single phase of deep green microcrystals in a 98% yield. It was characterised22 by IR spectra and elemental analyses, and the experimental data agreed with the literature.13 Synthesis of {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O (6) In a 85 mL TFM Teon vessel equipped with a temperature sensor and a magnetic stirrer were placed 0.61 mmol (0.542 g) of [Ru2 Cl(DPhF)3 (O2 CMe)] and 0.20 mmol (0.045 g) of trimesic acid. The vessel was sealed and the reaction mixture was heated for 45 min at 65 C in the microwave oven. Afterwards, it was left to cool at room temperature giving rise to the compound as a single phase of dark purple microcrystals. The crystals were ltered off, washed with methanol (5 mL) and diethyl ether (10 mL) and dried under vacuum. Yield: 75%. Compound 6 was characterised23 by IR spectra and elemental analyses with a resulting formula {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O. The results were compared with the ones previously obtained in the characterisation of monohydrated {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }H2 O synthesised by a conventional method.14

Conclusions
It has been proved that the use of microwave radiation allows the easy and clean substitution of the acetate groups in [Ru2 Cl(O2 CMe)4 ] by 1,3-diaryltriazenide, 1,3diarylformamidinate, or guanidinate ligands. In every case, the use of microwave activation promotes the total substitution of the acetate ligands by N,N-donor ligands. The selective substitution of the acetate group in [Ru2 Cl(DPhF)3 (O2 CMe)] by another carboxylate can also be achieved. The microwave methods described in this work lead to Ru2 4+ compounds when the ligand is a diaryltriazenide, Ru2 5+ complexes when the ligand employed is a 1,3-diarylformamidinate, and a Ru2 6+ compound when 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate is used. This fact could be due to an effect of the donor ability of the organic moiety: the higher the donor character of the equatorial ligand (hpp- > DArF- > DArT- ) is, the easier a high oxidation state in the nal compound can be reached.

Acknowledgements
We are grateful to Ministerio de Ciencia e Innovacion (MICINN), Comunidad de Madrid (CM) and Universidad Complutense de Madrid (UCM) (projects no. CTQ2008-00920, S2009/MAT-1467, and BSCH-UCM-2008-921073-4120824) for nancial support. Dr Perles acknowledges her Juan de la Cierva research contract from MICINN.

Notes and references

1 (a) F. A. Cotton and R. A. Walton, Multiple Bonds between Metal Atoms, 2nd ed., Wiley, New York, 1982; (b) F. A. Cotton, C. A. Murillo and R. A. Walton, Multiple Bonds between Metal Atoms, 3rd ed., Springer, New York, 2005. 2 (a) M. A. S. Aquino, Coord. Chem. Rev., 1998, 170, 141; (b) M. A. S. Aquino, Coord. Chem. Rev., 2004, 248, 1025.

3 M. Mikuriya, D. Yoshioka and M. Handa, Coord. Chem. Rev., 2006, 250, 2194. 4 See for example: (a) T. E. Vos and J. S. Miller, Angew. Chem., Int. Ed., 2005, 44, 2416; (b) M. C. Barral, S. Herrero, R. Jim nez-Aparicio, e M. R. Torres and F. A. Urbanos, Angew. Chem., Int. Ed., 2005, 44, 305; (c) W. Liu, E. N. Nfor, Y.-Z. Li, J.-L. Zuo and X.-Z. You, Inorg. Chem. Commun., 2006, 9, 923; (d) B. Liu, B.-L. Li, Y.-Z. Li, Y. Chen, S.-S. Bao and L.-M. Zheng, Inorg. Chem., 2007, 46, 8524; (e) B. S. Kennon, J.-H. Her, P. W. Stephens and J. S. Miller, Inorg. Chem., 2009, 48, 6117; (f) H. Miyasaka, N. Motokawa, S. Matsunaga, M. Yamashita, K. Sugimoto, T. Mori, N. Toyota and K. R. Dunbar, J. Am. Chem. Soc., 2010, 132, 1532. 5 See for example: (a) A. S. Blum, T. Ren, D. A. Parish, S. A. Trammell, M. H. Moore, J. G. Kushmerick, G.-L. Xu, J. R. Deschamps, S. K. Pollack and R. Shashidhar, J. Am. Chem. Soc., 2005, 127, 10010; (b) J.-W. Ying, D. R. Sobransingh, G.-L. Xu, A. E. Kaifer and T. Ren, Chem. Commun., 2005, 357; (c) D. Olea, R. Gonz lez-Prieto, J. L. a Priego, M. C. Barral, P. J. de Pablo, M. R. Torres, J. Gomez-Herrero, R. Jim nez-Aparicio and F. Zamora, Chem. Commun., 2007, 1591; e (d) A. K. Mahapatro, J. W. Ying, T. Ren and D. B. Janes, Nano Lett., 2008, 8, 2131; (e) L. Welte, R. Gonzalez-Prieto, D. Olea, M. R. Torres, J. L. Priego, R. Jimenez-Aparicio, J. Gomez-Herrero and F. Zamora, ACS Nano, 2008, 2, 2051; (f) B. Xi and T. Ren, C. R. Chim., 2009, 12, 321; (g) J.-W. Ying, I. P.-C. Liu, B. Xi, Y. Song, C. Campana, J.-L. Zuo and T. Ren, Angew. Chem. Int. Ed., 2010, 49, 954. 6 (a) M. Nuchter, B. Ondruschka, W. Bonrath and A. Gum, Green Chem., 2004, 6, 128; (b) B. A. Roberts and C. R. Strauss, Acc. Chem. Res., 2005, 38, 653; (c) C. R. Strauss and D. W. Rooney, Green Chem., 2010, 12, 1340. 7 (a) A. Loupy, Microwaves in Organic Synthesis, 1st ed., Wiley VCH, 2002; (b) J. P. Tierney and P. Lidstrom, ed. Microwave Assisted Organic Synthesis, Blackwell Publishing Ltd, Oxford, 2005; (c) C. O. Kappe, D. Dallinger and S. Murphree, ed. Practical Microwave Synthesis for Organic Chemists: Strategies, Instruments, and Protocols, Wiley-VCH, Weinheim, 2008; (d) K. Kranjc and M. Kocevar, Curr. Org. Chem., 2010, 14, 1050. 8 S. Herrero, R. Jim nez-Aparicio, J. Perles, J. L. Priego and F. A. e Urbanos, Green Chem., 2010, 12, 965. 9 K. D. Johnson and G. L. Powell, J. Organomet. Chem., 2008, 693, 1712. 10 (a) J. L. Bear, B. Han, S. Huang and K. M. Kadish, Inorg. Chem., 1996, 35, 3012; (b) F. A Cotton and T. Ren, Inorg. Chem., 1995, 34, 3190; (c) P. Angaridis, F. A. Cotton, C. A. Murillo, D. Villagr n and a X. Wang, Inorg. Chem., 2004, 43, 8290. 11 C. Lin, T. Ren, E. J. Valente, J. D. Zubkowski and E. T. Smith, Chem. Lett., 1997, 753. 12 M. C. Barral, S. Herrero, R. Jim nez-Aparicio, M. R. Torres and F. e A. Urbanos, Inorg. Chem. Commun., 2004, 7, 42. 13 (a) J. L. Bear, Y. Li, B. Han and K. M. Kadish, Inorg. Chem., 1996, 35, 1395; (b) F. A Cotton, C. A Murillo, X. Wang and C. C. Wilkinson, Inorg. Chim. Acta, 2003, 351, 191. 14 M. C. Barral, T. Gallo, S. Herrero, R. Jim nez-Aparicio, M. R. Torres e and F. A. Urbanos, Inorg. Chem., 2006, 45, 3639. 15 A. J. Lindsay, G. Wilkinson, M. Motevalli and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1987, 2723. 16 R. W. Mitchell, A. Spencer and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1973, 846. 17 R. M. J. Roberts, J. Org. Chem., 1949, 14, 277. 18 G. M. Sheldrick, SHELXS-97, Program for solution of crystal structures, University of Gottingen, Germany, 1997. 19 Elemental Analyses for 1 [Ru2 (C12 N3 H10 )4 ]: experimental C, 58.34%; H, 4.13%; N, 16.91%, calculated C, 58.41%; H, 4.08%; N, 17.03%. IR/cm-1 664 m, 686 vs, 755 vs, 775 m, 903 w, 1023 w, 1164 w, 1208 m, 1286 s, 1455 w, 1482 s, 1589 m, 3060 w. Two crystals of complex 1 were solved by single crystal X-ray diffraction (CCDC 814431 and 814432): in both cases the paddlewheel molecular species is identical, and the structures only differ in the solvent molecules present in the voids. They crystallise in the orthorhombic system, space group Pna21 , with a = 18.703(1), b = 25.891(2), and c = 9.8896(6) A, with a nal R factor of 0.0769 and a Goodness of Fit of 0.952 in the case of 1THF, and with a = 18.742(2), b = 25.884(2), and c = 9.8779(8) A, with a nal R factor of 0.0759 and a Goodness of Fit of 0.839 in the case of 1 with an unidentied disordered solvent. Elemental Analyses for 2 [Ru2 (C12 N3 H8 F2 )4 ]: experimental C, 50.98%; H, 3.01%;

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N, 14.48%, calculated C, 50.98%; H, 2.85%; N, 14.86%. IR/cm-1 667 m, 708 w, 720 w, 797 m, 811 m, 828 s, 884 w, 1009 w, 1092 m, 1148 s, 1192 s, 1202 s, 1217 s, 1282 m, 1294 m, 1312 m, 1492 vs, 1596 w, 3004 vw, 3078 vw. Compound 2 (CCDC 766373) crystallises in the monoclinic system, space group P21 /c, with a = 9.6596(4), b = 38.896(2), and c = 12.5248(5) A, and b = 102.989(1) , with a nal R factor of 0.0459 and a Goodness of Fit of 1.012. 20 Elemental Analyses for 3 [Ru2 Cl(C13 N2 H11 )4 ]: experimental C, 61.34%; H, 4.62%; N, 10.95%, calculated C, 61.32%; H, 4.35%; N, 11.00%. IR/cm-1 693 vs, 754 vs, 778 w, 936 w, 955 w, 1027 w, 1065 w, 1212 vs, 1323 ss, 1449 w, 1484 vs, 1532 vs, 1592 w, 2848 vw, 2950 vw, 3058 vw. Compound 3 (CCDC 814433) crystallises in the orthorhombic system, space group P4/ncc, with a = 15.028(2), b = 15.028(2), and c = 21.962(4) A, with a nal R factor of 0.0471 and a Goodness of Fit of 1.089. 21 Elemental Analyses for 4 [Ru2 Cl(C15 N2 H15 O2 )4 ]: experimental C, 57.24%; H, 4.92%; N, 8.70%, calculated C, 57.25%; H, 4.80%; N,

8.90%. IR/cm-1 693 w, 717 w, 730 w, 769 m, 790 m, 805 m, 825 s, 935 m, 1010 w, 1029 s, 1107 m, 1116 w, 1174 s, 1211 vs, 1240 s, 1291 m, 1338 m, 1368 w, 1437 w, 1455 w, 1500 vs, 1545 m, 1604 m, 2832 w, 2895 w, 2960 w. Compound 4 (CCDC 814434) crystallises in the orthorhombic system, space group Pccn, with a = 14.2592(8), b = 14.2608(8), and c = 30.417(2) A, with a nal R factor of 0.0778 and a Goodness of Fit of 0.987. 22 Elemental Analyses for 5 [Ru2 Cl2 (C7 N3 H12 )4 ]: experimental C, 40.59%; H, 5.66%; N, 19.98%, calculated C, 40.72%; H, 5.86%; N, 20.35%. IR/cm-1 726 m, 708 m, 751 s, 901 m, 1027 s, 1066 m, 1134 s, 1208 vs, 1274 s, 1306 s, 1384 s, 1438 s, 1464 s, 1526 vs, 2827 m, 2931 w. 23 Elemental Analyses for 6, {[Ru2 Cl(DPhF)3 ]3 (O2 C)3 C6 H3 }3H2 O: experimental C, 55.34%; H, 3.94%; N, 9.17%, calculated C, 55.41%; H, 3.99; N, 9.23%. IR/cm-1 689 vs, 730 s, 751 s, 775 m, 841 w, 939 m, 1002 w, 1026 m, 1076 m, 1112 w, 1155 w, 1214 vs, 1311 s, 1369 s, 1443 m, 1485 vs, 1527 vs, 1593 m, 3032 w.

1890 | Green Chem., 2011, 13, 18851890

This journal is The Royal Society of Chemistry 2011