Reaction of [Ru3(CO)12] with Phenazine: Synthesis of C-Metalated

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Reaction of [Ru3(CO)12] with Phenazine: Synthesis of C-Metalated Derivatives That Formally Arise from a C−H Oxidative Addition or a Long-Distance C-to-N Prototropy Javier A. Cabeza,* Pablo García-Á lvarez, and Vanessa Pruneda †

Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo−CSIC, E-33071 Oviedo, Spain S Supporting Information *

ABSTRACT: Three products, [Ru3(μ-H)(μ3-{(C6H4)(C6H3)N2})(CO)9] (1), [Ru4(μ4-{(C6H4)(C6H3)N2H})(μ-CO)(CO)10] (2), and [Ru6(μ5-{(C6H4)(C6H3)N2H})(μ-CO)3(CO)12] (3), have been prepared by treating [Ru3(CO)12] with phenazine. Compounds 2 and 3 are formed from compound 1 by stepwise addition of Ru(CO)n fragments. While compound 1 has a C-metalated ligand that arises from an oxidative addition of a phenazine C−H bond, compounds 2 and 3 contain a Cmetalated phenazine NH tautomer. In these complexes, the resulting ligands are attached to three (1), four (2), or five (3) metal atoms using different coordination modes.

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INTRODUCTION In recent years, pyridines,1−3 polypyridines,4−7 and other Nheterocycles8−11 have been shown to undergo metal-induced migrations of one of their H atoms to an N atom (C-to-N prototropic processes) that, generally, lead to complexes containing N-heterocyclic carbenes with NH moieties (some examples are given in Scheme 1). However, such processes have not hitherto been observed for aromatic diazines.

Scheme 2

Scheme 1

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The reaction of [Ru3(CO)12] with an equimolar amount of phenazine in THF at reflux temperature proved to be slow. The complete consumption of the ruthenium carbonyl was observed after 12 h. A chromatographic workup of the reaction mixture allowed the separation of [Ru3(μ-H)(μ3-{(C6H4)(C6H3)N2})(CO)9] (1), [Ru4(μ4-{(C6H4)(C6H3)N2H})(μ-CO)(CO)10] (2), and [Ru6(μ5-{(C6H4)(C6H3)N2H})(μ-CO)3(CO)12] (3), which were isolated as brown, red-brown, and dark brown

On the other hand, it has been reported that [Ru3(MeCN)2(CO)10]12 and [Ru3(CO)12]13−15 react with aromatic diazines, such as pyrimidine,12,13 pyrazine,12,14 quinoxaline,14 and 1,5naphthyridine,15 to give 1,2-cyclometalated hydrido decacarbonyl derivatives that arise from the oxidative addition of a ligand C−H bond (Scheme 2). We now report that phenazine, which has two benzoannulated rings that prevent any 1,2-cyclometalation reaction, reacts with [Ru3(CO)12] to give products that arise from processes that are unprecedented in the chemistry of phenazine, namely, a C−H oxidative addition and a C-to-N prototropy. © 2012 American Chemical Society

RESULTS AND DISCUSSION

Received: October 14, 2011 Published: January 12, 2012 941

dx.doi.org/10.1021/om200983a | Organometallics 2012, 31, 941−946

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solids, respectively (Scheme 3). They all have been characterized by X-ray diffraction and spectroscopic methods.

Table 1. Selected Interatomic Distances (Å) in Compounds 1, 2, and 3

Scheme 3

The molecular structure of compound 1 (Figure 1, Table 1) contains an Ru3 triangle that is spanned by a hydride, H100,

bond

1

2

3

Ru1−Ru2 Ru1−Ru3 Ru1−Ru6 Ru2−Ru3 Ru2−Ru4 Ru2−Ru5 Ru3−Ru4 Ru3−Ru5 Ru3−Ru6 Ru4−Ru5 Ru1−N1 Ru2−N1 Ru2−C1 Ru3−C1 Ru3−C2 Ru6−C1 Ru4−Cring (av) N1−C11 N1−C12 N2−C5 N2−C6 C1−C2 C1−C12 C2−C3 C3−C4 C4−C5 C5−C12 C6−C7 C6−C11 C7−C8 C8−C9 C9−C10 C10−C11

2.727(2) 2.881(2)

2.8746(7) 2.8103(7)

2.836(2)

2.8936(7) 2.9113(7)

2.20(1)

2.135(5) 2.186(5)

2.7360(6) 2.9481(7) 2.6946(7) 2.8259(7) 2.8690(7) 2.7981(7) 3.0047(7) 2.8290(7) 2.7990(7) 2.6973(7) 2.113(5) 2.209(5)

2.103(7)

2.324(6)

2.32(3) 1.442(9) 1.416(8) 1.38(1) 1.391(9) 1.437(9) 1.43(1) 1.41(1) 1.40(1) 1.418(9) 1.44(1) 1.38(1) 1.42(1) 1.39(1) 1.40(1) 1.40(1) 1.39(1)

2.201(6) 2.32(6) 1.469(8) 1.382(8) 1.366(8) 1.382(8) 1.431(9) 1.449(9) 1.41(1) 1.397(9) 1.420(9) 1.441(9) 1.395(9) 1.396(9) 1.37(1) 1.38(1) 1.378(9) 1.379(9)

2.12(1) 2.27(2) 2.52(1)

1.37(2) 1.33(2) 1.31(2) 1.35(2) 1.41(2) 1.46(2) 1.43(2) 1.34(2) 1.46(2) 1.44(2) 1.40(2) 1.46(2) 1.39(2) 1.40(2) 1.37(2) 1.42(2)

Figure 1. Molecular structure of compound 1 (ellipsoids set at 20% probability).

and capped by a ligand that results from the loss of an H atom from the phenazine C1 carbon atom. The ligand N1 atom is attached to Ru1, while the dehydrogenated carbon atom, C1, asymmetrically spans the hydride-bridged Ru2−Ru3 edge. The main plane of the heterocyclic ligand forms an angle with the Ru3 plane of 67.1(2)o. Such a deviation from perpendicularity is consequence of an interaction of the ligand C1C2 double bond with the Ru3 atom, which also forces the localization of the additional CC double bond of the benzo ring on the C3 and C4 carbon atoms. The four C−N bond distances are very similar, ranging from 1.31 to 1.37 Å. The cluster shell is completed with nine CO ligands. Therefore, the bridging ligand of compound 1 behaves as a five-electron donor. Compounds 2 (Figure 2, Table 1) and 3 (Figure 3, Table 1) comprise four and six Ru atoms, respectively. Both contain a phenazine NH tautomer that formally arises from the transfer of a hydrogen atom from the C1 carbon atom to the N2

Figure 2. Molecular structure of compound 2 (ellipsoids set at 40% probability). For clarity, the η6-coordination of the ligand to Ru4 is represented by a dashed line between this atom and the centroid of the coordinated ring.

nitrogen atom. In the case of 2, this ligand caps a regular Ru3 triangle in such a way that the N1 atom symmetrically spans the Ru1−Ru2 metallic edge, while the C1 carbon atom is terminally 942


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δ = 7.68 ppm in acetone-d6 (that of compound 3 could not be observed). For 2 and 3, the η6-coordination of a benzo ring is clearly indicated by their 1H and 13C resonances, which are displaced to lower frequencies than those of the remaining (uncoordinated) benzo group. In order to shed some light on mechanistic aspects of the processes that lead to compounds 2 and 3, we studied the thermolysis of compound 1 in refluxing THF in three different conditions, i.e., (a) in the absence of any additional reagent, (b) in the presence of one equivalent of phenazine, and (c) in the presence of one equivalent of [Ru3(CO)12]. The reactions were monitored by TLC, IR spectroscopy, and 1H NMR. The first two reactions led only to the progressive decomposition of compound 1 to phenazine and an untractable metal-containing material. The third reaction led to the complete consumption of compound 1 in 6.5 h and to the stepwise formation of compounds 2 and 3. These results confirm that compounds 1−3 are not formed from [Ru3(CO)12] and phenazine by independent reaction pathways and help explain the fact that the three complexes are observed when [Ru3(CO)12] is heated in solution with an equimolar amount of phenazine. As the formation of compound 1 from [Ru3(CO)12] and phenazine is slow, compound 1 coexists with an excess of [Ru3(CO)12] in the early stages of the reaction and can sequentially add one or three Ru(CO)n fragments (that are formed in hot solutions of [Ru3(CO)12]17) to give 2 and 3, respectively. Unfortunately, the mechanistic aspects of the prototropic process by which the phenazine NH tautomer (of 2) is formed from compound 1 are still very obscure. It is clear that the longdistance transfer of the hydride H atom of 1 to the uncoordinated N atom of the C-metalated phenazine ligand cannot be an intramolecular process. Therefore, such a transfer should occur intermolecularly, either directly (the hydride atom is transferred to the free N atom of a different molecule) or through a proton transporter (water, THF solvent, or free phenazine) and should be accompanied by the addition of a Ru(CO)n fragment, since only extensive decomposition was obtained when 1 was heated without [Ru3(CO)12] in the presence and in the absence of free phenazine. A remarkable feature of the process that leads to compound 2 is that the prototropy takes place between atoms that are separated by many bonds. Such a long-distance proton transfer is unprecedented in transition metal complexes, in which prototropy is generally an intramolecular processes.1c The tautomerization of N-coordinated imidazoles to N-heterocyclic carbene ligands, promoted by additional reagents, has also been reported,11 but, in all these cases, the prototropy processes take place between C and N atoms that are close to each other. In conclusion, compound 1 arises from the oxidative addition of a phenazine C−H bond (among other processes such as CO ligand substitution), while compound 2 results from compound 1 through a combination of an Ru(CO)n fragment addition and a prototropic process that transfers the hydride H atom to the uncoordinated N atom of the C-metalated phenazine ligand. A subsequent incorporation of two Ru(CO)n to the tetranuclear compound 2 leads to the hexanuclear derivative 3, which maintains the same C-metalated NH phenazine tautomer as 2. Both the C−H oxidative addition and any NH-containing tautomers of phenazine are unprecedented in the coordination chemistry of this heterocycle, where, to date, only metal complexes containing terminal18 or bridging19 phenazine can be found.

Figure 3. Molecular structure of compound 3 (ellipsoids set at 20% probability). For clarity, the η6-coordination of the ligand to Ru4 is represented by a dashed line between this atom and the centroid of the coordinated ring.

bound to Ru3. The fourth metal atom of 2, Ru4, is attached to Ru2 and η6-bonded to the benzo ring that contains the C1 carbon atom. In 3, four Ru atoms (Ru1, Ru2, Ru3, and Ru6) are disposed in a butterfly arrangement in which the hinge is defined by Ru1 and Ru3 atoms. Two wing edges of this butterfly, Ru1−Ru2 and Ru3−Ru6, are respectively spanned by the N1 and C1 atoms of the phenazine NH tautomer, and the Ru2−Ru3 edge is also tetrahedrically attached to a diruthenium fragment, Ru4−Ru5, that is also η6-bonded through the Ru4 atom to the benzo ring that contains the C1 carbon atom. The edge-bridging character of the coordinated benzo group of compound 3 is unusual.16 As expected, the C−C bond distances of the η6-coordinated benzo group of 2 and 3 are longer than those of the remaining (uncoordinated) benzo group. The ligand of these two complexes is not planar but slightly folded about the N1−N2 line, the dihedral angle between the main planes of the benzo rings being 13.7(1)o in 2 and 9.3(1)o in 3. The sp3 character of the bridging N1 atom of 2 and 3 is responsible for a lengthening (in the range 0.04−0.11 Å) of the N1−C distances with respect to those of compound 1, in which the N1 atom is sp2 hybridized. The HN2−C distances of 2 and 3 (in the range 1.37−1.39 Å) and the bond angles around the N2 nitrogen atom approximate those of an sp2 hybridization, indicating that this nitrogen atom is engaged in a delocalized electronic system that connects the two benzo groups. The cluster shell is completed with one bridging and 10 terminal CO ligands in the case of 2 and three bridging and 12 terminal CO ligands in the case of 3. Therefore, the bridging ligand of 2 and 3 behaves as a 10-electron donor. The solution IR and NMR spectra of 1−3 are in complete agreement with their solid-state structures. Their IR spectra in CH2Cl2 clearly show that the three complexes have terminal CO ligands (νCO absorptions in the 2089−1928 cm−1 range) but only two (2 and 3) have bridging CO ligands (νCO absorptions in the 1873−1809 cm−1 range). The coordination of the C2 carbon 1 is indicated by the NMR resonances of the C2−H group (δH = 5.84 ppm, δC = 108.3 ppm, in CD2Cl2), which are displaced to lower frequencies than those of the remaining (uncoordinated) C−H groups. Its hydride ligand is observed in the 1H NMR spectrum as a singlet at δ = −14.56 ppm. The 1H resonance of the N−H group of 2 is observed at 943


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Table 2. Crystal, Measurement, and Refinement Data for the Compounds Studied by X-ray Diffraction

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formula fw cryst syst space group a, Å b, Å c, Å α, deg β, γ, deg V, Å3 Z F(000) Dcalcd, g cm−3 μ(Cu Kα), mm−1 cryst size, mm T, K θ range, deg min./max. h, k, l no. collected reflns no. unique reflns no. reflns with I > 2σ(I) no. params/restraints GOF (on F2) R1 (on F, I > 2σ(I)) wR2 (on F2, all data) min./max. Δρ, e Å−3

1

2·CH2Cl2

3·C6H14

C21H8N2O9Ru3 735.50 monoclinic C2/c 10.6002(6), 15.8393(5) 26.947(1) 90 93.510(1) 90 4515.8(4) 8 2816 2.164 16.560 0.08 × 0.06 × 0.01 293(2) 3.29 to 59.99 −10/9, −13/17, −30/19 5495 3030 1948 310/0 0.926 0.057 0.123 −0.870/0.845

C23H8N2O11Ru4·CH2Cl2 977.52 triclinic P1̅ 10.0952(4) 11.9576(7) 12.6553(7) 103.652(5) 110.860(4) 90.282(4) 1380.5(3) 2 932 2.352 19.751 0.13 × 0.03 × 0.01 100(2) 3.82 to 69.99 −12/11, −14/14, 0/15 5092 5092 4264 391/1 1.002 0.047 0.132 −2.169/1.469

C27H8N2O15Ru6·C6H14 1292.95 monoclinic P21/c 9.4598(1) 14.6720(1) 27.4455(2) 90 97.234(1) 90 3778.95(3) 4 2472 2.273 19.570 0.19 × 0.06 × 0.03 123(2) 3.25 to 67.99 −8/11, −17/15, −29/32 17 089 6877 6037 507/0 1.052 0.045 0.119 −1.420/1.584

6.8, 0.9 Hz, 1H, CH), 7.60 (dd, J = 9.0, 0.9 Hz, 1H, CH), 7.30 (dd, J = 9.1, 5.2 Hz, 1H, CH), 5.84 (d, J = 5.2 Hz, 1H, CH), −14.56 (s, 1H, μ-H). 13 1 C{ H} and DEPT NMR (CD2Cl2, 293 K): δ 202.6, 199.3, 197.7, 195.4 (COs), 162.8 (C), 144.4 (C), 142.3 (C), 142.2 (C), 132.8 (CH), 132.6 (CH), 130.8 (CH), 130.4 (CH), 130.1 (CH), 127.6 (CH), 124.8 (C), 108.3 (CH). Analytical Data for 2. Anal. Calcd for C23H8N2O11Ru4 (892.6): 30.95; H, 0.90; N, 3.14. Found: C, 31.02; H, 0.96; N, 3.09. (+)-FAB MS: no satisfactory spectrum could be obtained. IR (CH2Cl2): νCO 2079 (m), 2046 (s), 2020 (vs), 1997 (w), 1951 (w, br), 1809 (vw, br). 1 H NMR (acetone-d6, 293 K): δ 7.68 (s, 1H, NH), 6.93 (dd, J = 7.6, 2.0 Hz, 1H, CH), 6.82−6.72 (m, 2H, CH), 6.66 (dd, J = 6.8, 6.0 Hz, 1H, CH), 6.19 (dd, J = 6.8, 1.6 Hz, 1H, CH), 6.13 (dd, J = 7.2, 2.4 Hz, 1H, CH), 5.76 (dd, J = 6.0, 1.6 Hz, 1H, CH). 13C{1H} and DEPT NMR (acetone-d6, 293 K): δ 233.0, 218.5, 209.1, 203.6, 201.1, 199.9, 199.8, 195.9, 191.4 (COs), 147.6 (C), 131.1 (CH), 127.2 (C), 126.6 (CH), 122.4 (CH), 120.9 (C), 113.9 (CH), 111.6 (C), 110.7 (C), 98.0 (CH), 95.8 (CH), 87.0 (CH). Analytical Data for 3. Anal. Calcd for C27H8N2O15Ru6 (1206.8): 26.87; H, 0.67; N, 2.32. Found: C, 26.95; H, 0.72; N, 2.26. (+)-FAB MS: m/z 1208 [M]+. IR (CH2Cl2): νCO 2089 (m), 2043 (vs), 2013 (s), 1989 (m), 1969 (w, sh), 1928 (w, br), 1873 (vw, br), 1822 (w, br). 1 H NMR (CD2Cl2, 293 K): δ 87.42 (dd, J = 8.3, 1.2 Hz, 1H, CH), 7.29 (dd, J = 6.2, 1.1Hz, 1H, CH), 7.09 (ddd, J = 8.3, 7.4, 1.4 Hz, 1H, CH), 6.96 (ddd, J = 7.8, 7.4, 1.2 Hz, 1H, CH), 6.52 (dd, J = 6.2, 6.0 Hz, 1H, CH), 6.46 (dd, J = 7.8, 1.4 Hz, 1H, CH), 3.77 (dd, J = 6.0, 1.1 Hz, 1H, CH) (NH proton not observed). 13C{1H} and DEPT NMR (acetoned6, 293 K): δ 235.3, 223.0, 211.9, 209.1 200.4, 198.2, 196.2, 195.1, 193.9, 192.4, 189.9, 185.9, 184.1 (COs), 144.9 (C), 127.5 (CH), 126.7 (CH), 125.7 (CH), 125.4 (C), 117.5 (C), 116.0 (CH), 114.5 (C), 110.3 (CH), 96.5 (C), 90.8 (CH), 79.5 (CH). Reaction of Compound 1 with [Ru3(CO)12]. A THF solution (20 mL) of compound 1 (30 mg, 0.041 mmol) and [Ru3(CO)12] (30 mg, 0.047 mmol) was stirred at reflux temperature while small aliquots were periodically analyzed by IR spectroscopy and spot TLC (silica gel). After 4 h, compound 2 started to be clearly observed by TLC.

EXPERIMENTAL SECTION

General Data. Solvents were dried over sodium diphenyl ketyl (hydrocarbons, THF) or CaH2 (dichloromethane) and distilled under nitrogen before use. The reactions were carried out under nitrogen, using Schlenk-vacuum line techniques, and were routinely monitored by solution IR spectroscopy (carbonyl stretching region) and spot TLC on silica gel. The reaction products were vacuum-dried for several hours prior to being weighted and analyzed. IR spectra were recorded in solution on a Perkin-Elmer Paragon 1000X spectrophotometer. NMR spectra were run on a Bruker DPX-300 instrument using the solvent peaks as internal standards. Microanalyses were obtained from the University of Oviedo Analytical Service. FAB mass spectra were obtained from the University of A Coruña Mass Spectrometric Service; data given refer to the most abundant molecular ion isotopomer. Reaction of [Ru3(CO)12] with Phenazine. A THF solution (50 mL) of [Ru3(CO)12] (100 mg, 0.156 mmol) and phenazine (31 mg, 0.172 mmol) was stirred at reflux temperature for 12 h. The color changed from orange to dark brown. The solvent was removed under reduced pressure, the residue was extracted into dichloromethane (1 mL), and this solution was transferred onto a chromatography column (2 × 15 cm) packed with silica gel in hexane. Hexane and subsequently hexane−dichloromethane (4:1) eluted trace amounts of [Ru3(CO)12] and a green uncharacterized compound. Hexane−dichloromethane (1:1) eluted compound 1, which was isolated as a brown solid (25 mg, 22%). Hexane−dichloromethane (1:3) eluted compound 2, which was isolated as a red-brown solid (25 mg, 19%). Subsequent elution of the column with dichloromethane eluted compound 3 (10 mg, 11%). A dark residue remained uneluted at the top of the column. Analytical Data for 1. Anal. Calcd for C21H8N2O9Ru3 (735.5): 34.29; H, 1.10; N, 3.81. Found: C, 34.34; H, 1.14; N, 3.77. (+)-FAB MS: m/z 737 [M]+. IR (CH2Cl2): νCO 2080 (w), 2052 (vs), 2031 (s), 2002 (m), 1987 (w, sh), 1972 (vw, sh), 1960 (vw, sh). 1H NMR (CD2Cl2, 293 K): δ 8.54 (d, J = 9.1 Hz, 1H, CH), 8.19 (dd, J = 8.5, 0.9 Hz, 1H, CH), 8.08 (ddd, J = 8.5, 6.8, 0.9 Hz, 1H, CH), 7.86 (ddd, J = 9.0, 944


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After 6 h, all starting material 1 had disappeared and the TLC plates clearly showed the spots of compounds 2, 3, and [Ru3(CO)12] (together with two pale brown bands that decomposed on the silica). At this point, the solvent was removed under reduced pressure and the residue was analyzed by 1H NMR in acetone-d6. Integration of the corresponding spectrum confirmed the presence of 2, 3, and free phenazine in a ca. 1.4:1.6:1.0 mol ratio. X-ray Diffraction Analyses. Crystals of 1, 2·CH2Cl2, and 3·C6H14 were analyzed by X-ray diffraction. A selection of crystal, measurement, and refinement data is given in Table 2. Diffraction data were collected on an Oxford Diffraction Xcalibur Onyx Nova single-crystal diffractometer. Empirical absorption corrections for 1 and 3·C6H14 were applied using the SCALE3 ABSPACK algorithm as implemented in CrysAlisPro RED.20 The XABS221 empirical absorption correction was applied for 2·CH2Cl2. The structures were solved using the program SIR-97.22 Isotropic and full matrix anisotropic least-squares refinements were carried out using SHELXL.23 All non-H atoms were refined anisotropically. The hydride ligand of 1 was calculated with XHYDEX.24 The remaining hydrogen atoms, except the NH of compound 2, were set in calculated positions and refined riding on their parent atoms. The refinement of 1 was carried out applying a low 2θ cut-off as the weakly diffracting crystal gave essentially no diffraction above 2θ = 120°. The molecular plots were made with the PLATON program package.25 The WINGX program system26 was used throughout the structure determinations. CCDC deposition numbers: 846463 (1), 846464 (2·CH2Cl2), and 848652 (3·C6H14).

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format for the compounds studied by X-ray diffraction and 1H and 13C NMR spectra of 1−3. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected].

ACKNOWLEDGMENTS This work has been supported by the European Union (FEDER grants and Marie Curie action FP7-2010-RG268329) and the Spanish MICINN (projects CTQ201014933 and DELACIERVA-09-05). Fellowships from the University of Oviedo and Principado de Asturias (to V.P.) are gratefully acknowledged.

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REFERENCES

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Reaction of [Ru3(CO)12] with Phenazine: Synthesis of C-Metalated

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