General Synthesis of (Salen)ruthenium(III) Complexes via N???N Coupling of (Salen)ruthenium(VI) Nitrides

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General Synthesis of (Salen)ruthenium(III) Complexes via N · · · N

Coupling of (Salen)ruthenium(VI) Nitrides

Wai-Lun Man,†Hoi-Ki Kwong,† William W. Y. Lam,†Jing Xiang,†Tsz-Wing Wong,†Wing-Hong Lam,† Wing-Tak Wong,‡_{Shie-Ming Peng,}§ _{and Tai-Chu Lau*},†

Contribution from the Department of Biology and Chemistry, City UniVersity of Hong Kong, Tat Chee AVenue, Kowloon Tong, Hong Kong, China, Department of Chemistry, UniVersity of Hong Kong, Pokfulam Road, Hong Kong, China, and Department of Chemistry, National Taiwan UniVersity, Taipei 106, Taiwan

Received February 13, 2008

Reaction of [RuVI_(N)(L1_)(MeOH)]+

(L1_{) N,N′-bis(salicylidene)-o-cyclohexylenediamine dianion) with excess pyridine}

in CH3CN produces [RuIII_(L1_)(py)2]+

and N2. The proposed mechanism involves initial equilibrium formation of

[RuVI_(N)(L1_)(py)]+

, which undergoes rapid N · · · N coupling to produce [(py)(L1_)RuIII_NtN-RuIII_(L1_)(py)]2+_{; this is}

followed by pyridine substituion to give the final product. This ligand-induced N · · · N coupling of RuVI

tN is utilized

in the preparation of a series of new ruthenium(III) salen complexes, [RuIII_(L)(X)2](

(L ) salen ligand; X ) H2O,

1-MeIm, py, Me2SO, PhNH2,t_{BuNH2, Cl}

-or CN-). The structures of [RuIII_(L1_{)(NH2Ph)2](PF6) (6), K[Ru}III_(L1_)(CN)2]

(9), [RuIII_(L2_{)(NCCH3)2][Au}I_{(CN)2] (11) (L}2_{) N,N′-bis(salicylidene)-o-phenylenediamine dianion) and [N}n_Bu4][RuIII_(L3_)Cl2]

(12) (L3) N,N′-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Introduction

Metal complexes bearing salen-type ligands have played important roles in the development of coordination chemistry for over half a century. In particular, manganese salen complexes have been widely used as catalysts for alkene

epoxidation.1–7 _{Recently, a number of ruthenium salen}

complexes have also been found to be active catalysts in

various organic transformations such as cyclopropanation,8–11

epoxidation,12–15aziridination,16–18 sulfimidation,19–21 and

Diels-Alder reactions22,23(Scheme 1).

These catalysts have the general formula

[Ru(salen)(X)-(Y)]n+_{, where X or Y is a nitrosyl,}12,23–33

carbonyl,16–21,34,35

phosphine,8,9,15,22,36–40or pyridine group.10,11However, there

* To whom correspondence should be addressed: Email: bhtclau@ cityu.edu.hk.

†_{City University of Hong Kong.} ‡_{University of Hong Kong.} §_{National Taiwan University.}

(1) Jacobsen, E. N. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 159-202.

(2) Jacobson, E. N. In ComprehensiVe Organometallic Chemistry II; Hegedus, L. S., Ed.; Elsevier: New York, 1995, pp 1097-1135.

(3) Jacobson, E. N.; Wu, M. H. In ComprehensiVe Asymmetric Catalysis II; Jacobson, E. N., Pfaltz, A., Yamamoto, H., Ed.; Springer: Berlin, 1999; pp 649-67.

(4) Katsuki, T. Coord. Chem. ReV. 1995, 140, 189–214.

(5) Katsuki, T. J. Mol. Catal. A. 1996, 113, 87–107.

(6) Samsel, E. G.; Srinivasan, K.; Kochi, J. K. J. Am. Chem. Soc. 1985, 107, 7606–7617.

(7) Srinivasan, K.; Michaud, P.; Kochi, J. K. J. Am. Chem. Soc. 1986, 108, 2309–2320.

(8) Li, G. Y.; Zhang, J.; Chan, P. W. H.; Xu, Z. J.; Zhu, N.; Che, C. M. Organometallics 2006, 25, 1676–1688.

(9) Miller, J. A.; Gross, B. A.; Zhuravel, M. A.; Jin, W.; Nguyen, S. T. Angew. Chem., Int. Ed. 2005, 44, 3885–3889.

(10) Miller, J. A.; Hennessy, E. J.; Marshall, W. J.; Scialdone, M. A.; Nguyen, S. T. J. Org. Chem. 2003, 68, 7884–7886.

(11) Miller, J. A.; Jin, W.; Nguyen, S. T. Angew. Chem., Int. Ed. 2002, 41, 2953–2956.

(12) Nakata, K.; Takeda, T.; Mihara, J.; Hamada, T.; Irie, R.; Katsuki, T. Chem.sEur. J. 2001, 7, 3776–3782.

(13) Kureshy, R. I.; Khan, N. H.; Abdi, S. H. R. J. Mol. Catal. A. 1995, 96, 117–122.

(14) Kureshy, R. I.; Khan, N. H.; Abdi, S. H. R.; Bhatt, A. K. J. Mol. Catal. A. 1996, 110, 33–40.

(15) Leung, W. H.; Che, C. M. Inorg. Chem. 1989, 28, 4619–4622. (16) Kawabata, H.; Omura, K.; Uchida, T.; Katsuki, T. Chem. Asian. J.

2007, 2, 248–256.

(17) Kawabata, H.; Omura, K.; Katsuki, T. Tetrahedron Lett. 2006, 47, 1571–1574.

(18) Omura, K.; Uchida, T.; Irie, R.; Katsuki, T. Chem. Commun. 2004, 2060–2061.

(19) Murakami, M.; Uchida, T.; Saito, B.; Katsuki, T. Chirality 2003, 15, 116–123.

(20) Uchida, T.; Tamura, Y.; Ohba, M.; Katsuki, T. Tetrahedron Lett. 2003, 44, 7965–7968.

(21) Tamura, Y.; Uchida, T.; Katsuki, T. Tetrahedron Lett. 2003, 44, 3301– 3303.

(22) Chow, C. P.; Shea, K. J. J. Am. Chem. Soc. 2005, 127, 3678–3679.

(23) Odenkirk, W.; Rheingold, A. L.; Bosnich, B. J. Am. Chem. Soc. 1992, 114, 6392–6398.

Inorg. Chem. 2008, 47, 5936-5944

5936 Inorganic Chemistry, Vol. 47, No. 13, 2008 10.1021/ic800263n CCC: $40.75  2008 American Chemical Society

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are no general methods for the preparation of these catalysts; each complex has to be prepared by a different method, as shown in eqs 1-4. [Ru(NO)Cl3] 98 salen 2-DMF, 110° C [Ru(salen)(NO)Cl] (1) [Ru(PPh3)3Cl2] 98 salen 2-refluxing MeOH [Ru(salen)(PPh3)Cl] (2) [Ru(salen)(PPh₃)₂] 98 CO CH2Cl2 [Ru(salen)(CO)] (3) [Ru(p - cymene)Cl₂]₂98 3,5-t_Bu 4salchda 2-LDA, py, THF [Ru(3,5-t Bu4salchda)(py)2] (4)

We have reported that the ruthenium(VI) nitrido species,

[RuVI_(N)(L1_)(MeOH)]+

(1), can be readily prepared from

[Nn_Bu4][RuVI_{(N)Cl4]. This species undergoes facile}

ligand-induced N · · · N coupling as represented by eq 5 (X is a

neutral ligand in this case).41

[RuVI(N)(L1)(MeOH)]++ 2X f [RuIII(L1)(X)2]

+₊

MeOH +1

2N2 (5)

In this work, we make use of this N · · · N coupling reaction to synthesize a series of new ruthenium(III) complexes bearing various salen ligands that are potential catalysts for organic transformations. The structures of the salen ligands used in this work are shown in Figure 1.

Experimental Section

Materials. [RuVI_(N)(L1_)(MeOH)](PF

6) (1),41[NnBu4][RuVI

(N)-Cl4],42and [RuIII(L1)(OH2)2](PF6)43(2) were prepared by literature

procedures. The Schiff base ligands, H2L1, H2L2, and H2L3(L1, L2

and L3 _{) bis(salicylidene)-o-cyclohexylenediamine,}

N,N′-bis(salicylidene)-o-phenylenediamine, and N,N ′-bis(salicylidene-)ethylenediamine dianion respectively) were synthesized by con-densation of salicylaldehyde with the corresponding diamines in refluxing ethanol.n_Bu

4NPF6(Aldrich) was recrystallized three times

from boiling ethanol and dried in vacuo at 120 °C for one day. Acetonitrile (Aldrich) for electrochemistry was distilled over calcium hydride. All other chemicals were of reagent grade and used without further purification. All manipulations were performed without precaution to exclude air or moisture unless otherwise stated.

Physical Measurements. IR spectra were obtained as KBr discs using a Nicolet 360 FTIR spectrophotometer.1_{H NMR spectra were}

recorded on a Varian (300 MHz) FT NMR spectrometer. The chemical shifts (ppm) were reported with reference to tetrameth-ylsilane (TMS). UV-vis spectra were recorded with a PerkinElmer Lamda 19 spectrophotometer in 1 cm quartz cuvettes. Elemental analysis was performed using an Elementar Vario EL Analyzer. Magnetic measurements were performed at room temperature using a Sherwood magnetic balance (Mark II). Conductivity measure-ments were done with a Cole-Parmer 01481-61 conductivity meter. Electrospray ionization mass spectrometry (ESI-MS) were per-formed with a PE-SCIEX API 300 triple quadruple mass spec-trometer. Cyclic voltammetry measurements were performed with a PAR model 273 potentiostat using a glassy carbon working electrode, a Ag/AgNO3(0.1 M in CH3CN) reference electrode, a

platinum wire counter electrode with ferrocene (FeCp2) as the

internal standard.

Preparations. [RuIII_(L1_)(1-MeIm)

2](PF6) (3). A green solution

of 1 (120 mg, 0.20 mmol) in 1-methylimidazole (2 mL) was stirred for 1 day. Slow addition of diethyl ether (50 mL) produced a green precipitate, which was filtered and then air-dried. Yield: (82%). IR (KBr, cm-1): ν(CdN) 1593; ν(P-F) 845. Anal. Calcd for C28H32N6O2PF6Ru: C, 46.03; H, 4.41; N, 11.50. Found: C, 45.87;

H, 4.56; N, 11.37. UV-vis (CH3CN): λmax [nm] (ε

[mol-1dm3_cm-1_{]) 680 (4955), 497 (1940), 388 (17 540), 343sh}

(12 890), 234sh (44 590), 214 (49 270). ESI-MS: m/z ) 586 (M+)

µeff) 1.96 µB.

[RuIII_(L1_)(py)

2](PF6) (4). The green solid was prepared by a

procedure similar to that for 3 using pyridine. Yield: (76%). IR (KBr, cm-1): ν(CdN) 1597; ν(P-F) 845. Anal. Calcd for (24) Nakamura, Y.; Egami, H.; Matsumoto, K.; Uchida, T.; Katsuki, T.

Tetrahedron 2007, 63, 6383–6387.

(25) Sun, W.; Yu, B.; Ku¨hn, F. E. Tetrahedron Lett. 2006, 47, 1993–1996.

(26) Shimizu, H.; Onitsuka, S.; Egami, H.; Katsuki, T. J. Am. Chem. Soc. 2005, 127, 5396–5413.

(27) Egami, H.; Onitsuka, S.; Katsuki, T. Tetrahedron Lett. 2005, 46, 6049– 6052.

(28) Irie, R.; Katsuki, T. Chem. Rec. 2004, 4, 96–109.

(29) Sauve, A. A.; Groves, J. T. J. Am. Chem. Soc. 2002, 124, 4770–4778.

(30) Bordini, J.; Hughes, D. L.; Da Motta Neto, J. D.; da Cunha, C. J. Inorg. Chem. 2002, 41, 5410–5416.

(31) Works, C. F.; Jocher, C. J.; Bart, G. D.; Bu, X.; Ford, P. C. Inorg. Chem. 2002, 41, 3728–3739.

(32) Works, C. F.; Ford, P. C. J. Am. Chem. Soc. 2000, 122, 7592–7593.

(33) Ellis, W. W.; Odenkirk, W. Chem. Commun. 1998, 1311–1312.

(34) Viswanathamurthi, P.; Natarajan, K. Transition Met. Chem. 1999, 24, 638–641.

(35) Khan, M. M. T.; Srinivas, D.; Kureshy, R. I.; Khan, N. H. Inorg. Chem. 1990, 29, 2320–2326.

(36) Syukri, S.; Sun, W.; Ku¨hn, F. E. Tetrahedron Lett. 2007, 48, 1613– 1617.

(37) Venkatachalam, G.; Ramesh, R. Inorg. Chem. Commun. 2005, 8, 1009– 1013.

(38) Ramesh, R. Inorg. Chem. Commun. 2004, 7, 274–276.

(39) Liang, J. L.; Yu, X. Q.; Che, C. M. Chem. Commun. 2002, 124–125.

(40) Thornback, J. R.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1978, 110–115.

(41) Man, W. L.; Tang, T. M.; Wong, T. W.; Lau, T. C.; Peng, S. M.; Wong, W. T. J. Am. Chem. Soc. 2004, 126, 478–479.

(42) Griffith, W. P.; Pawson, D. J. Chem. Soc., Dalton Trans. 1973, 1315– 1320.

(43) Wong, C. Y.; Man, W. L.; Wong, C.; Kwong, H. L.; Wong, W. Y.; Lau, T. C. Organometallics 2008, 27, 324–326.

Scheme 1. Examples of Ruthenium Salen Complexes as Active Catalysts in Organic Synthesis

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C30H30N4O2PF6Ru: C, 49.73; H, 4.17; N, 7.73. Found: C, 49.60;

H, 4.19; N, 7.64. UV-vis (CH3CN): λmax[nm] (ε [mol-1dm3cm-1])

723 (4650), 373 (16 490), 235 (43 650), 215 (41 510). ESI-MS:

m/z ) 580 (M+). µeff) 1.90 µB.

[RuIII_(L1_)(Me

2SO)2](PF6) (5). The green solid was prepared by

a procedure similar to that for 3 using Me2SO. Yield: (66%). IR

(KBr, cm-1): ν(CdN) 1599; ν(SdO) 1017; ν(P-F) 840. Anal. Calcd for C24H32N2O4S2PF6Ru: C, 39.89; H, 4.46; N, 3.88. Found:

C, 40.10; H, 4.41; N, 4.10. UV-vis (CH3CN): λmax [nm] (ε

[mol-1dm3_cm-1_{]) 734 (5015), 481 (1660), 332 (16 960), 232}

(43 780). ESI-MS: m/z ) 578 (M+). µeff) 2.07 µB.

[RuIII_(L1_)(NH

2Ph)2](PF6) (6). Aniline (0.32 mL, 3.52 mmol)

was added to a solution of 2 (100 mg, 0.16 mmol) in ethanol (15 mL). The green solution was refluxed for 1.5 h and then concentrated to ca. 1 mL. Slow addition of diethyl ether gave a green precipitate, which was recrystallized from acetone/diethyl ether. Yield: 51%. Single crystals suitable for X-ray crystallography were obtained by slow diffusion of diethyl ether into an acetone solution of the compound. IR (KBr, cm-1): ν(N-H) 3311, 3278;

ν(CdN) 1602; ν(P-F) 835. Anal. Calcd for C32H34N4O2PF6Ru:

C, 51.06; H, 4.55; N, 7.44. Found: C, 51.23; H, 4.62; N, 7.21. UV-vis (CH3CN): λmax[nm] (ε [mol-1dm3cm-1]) 705 (4880), 492

(1870), 363 (14 530), 346 (14 150), 233 (47 960), 202 (56 570). ESI-MS: m/z ) 608 (M+). µeff) 1.86 µB.

[RuIII_(L1_)(NH

2tBu)2](PF6) (7). The green solid was prepared by

a procedure similar to that for 6 using tert-butylamine (0.34 mL, 3.25 mmol). Yield: (40%). IR (KBr, cm-1): ν(N-H) 3300, 3244;

ν(C)N) 1600; ν(P-F) 849. Anal. Calcd. for C28H42N4O2PF6Ru:

C, 47.19; H, 5.94; N, 7.86. Found: C, 47.15; H, 5.75; N, 7.81. UV-vis (CH3CN): λmax[nm] (ε [mol-1dm3cm-1]) 670 (5920), 497

(2510), 387 (20 100), 366 (17 260), 234 (42 970), 217 (44 440) ESI-MS: m/z ) 568 (M+). µeff) 2.02 µB.

[Nn_Bu

4][RuIII(L1)Cl2] (8). [NnBu4Cl] (0.55 g, 2.0 mmol) was

added to an orange solution of 1 (120 mg, 0.2 mmol) in acetone (20 mL) and refluxed for 1 day. The green solution was then concentrated to ca. 1 mL. Addition of diethyl ether (20 mL) gave a green solid, which was recrystallized from CH2Cl2/Et2O. Yield:

(70%). IR (KBr, cm-1): ν(CdN) 1597. Anal. Calcd for C36H56N3O2Cl2Ru · CH2Cl2: C, 54.48; H, 7.19; N, 5.08. Found: C, 54.54; H, 6.91; N, 4.93. UV/vis (CH3CN): λmax [nm] (ε [mol-1dm3_cm-1_{]) 645 (5120), 514 (2395), 415 (21 930), 346} (11 850), 292 (8110), 238 (47 600), 221 (47 360). ESI-MS: m/z ) 494 (M-). µeff) 2.06 µB. K[RuIII_(L1_)(CN)

2] · H2O (9). KCN (130 mg, 2 mmol) was added

to an orange solution of 1 (123 mg, 0.2 mmol) in methanol (50 mL), and the mixture was stirred for 3 h at room temperature. Slow evaporation of the resulting green solution afforded dark green single crystals suitable for X-ray crystallography. Yield: 52%. IR (KBr, cm-1): ν(CtN) 2090; ν(CdN) 1598. Anal. Calcd for C22H22N4O3KRu: C, 49.80; H, 4.18; N, 10.56. Found: C, 49.95; H,

4.33; N, 10.37. ESI-MS: m/z ) 474 (M-). µeff) 1.97 µB.

[RuVI_(N)(L2_{)Cl] (10a). 2,6-dimethylpyridine (0.2 mL) was added}

dropwise to a solution of [Nn_Bu

4][RuVI(N)Cl4] (0.2 g, 0.4 mmol)

and H2L2(0.13 g, 0.4 mmol) in CH2Cl2(20 mL). The deep-brown

solution was stirred at room temperature for 0.5 h. The resulting brown solid was collected, washed with CH2Cl2, diethyl ether and

then air-dried. Yield: (80%).1_{H NMR (300 MHz, CD}

3OD): δ7.18

(t, 2H), 7.48 (d, 2H), 7.74 (m, 2H), 7.85 (m, 2H), 8.01 (d, 2H), 8.49 (m, 2H), 9.89 (s, 2H). IR (KBr, cm-1): ν(Rut14_{N) 1036;}

ν(Rut15_{N) 1006. Anal. Calcd for C}

20H14N3O2ClRu: C, 51.67; H,

3.01; N, 9.04. Found: C, 51.41; H, 3.12; N, 8.89. ESI-MS: m/z ) 430 (M+- Cl). Conductivity in CH3OH: Λ) 53 Ω-1cm2mol-1.

[RuVI_(N)(L2_)(MeOH)](ClO

4) (10b). 10a (0.186 g, 0.4 mmol)

was dissolved in methanol (30 mL) and silver p-toluenesulfonate (AgOTs) (0.112 g, 0.4 mmol) was added. The mixture was stirred at room temperature for 0.5 h and then filtered to remove AgCl. To the concentrated filtrate excess LiClO4(0.1 g, 0.9 mmol) was

added and the deep reddish-brown solution was cooled in ice. The resulting brick-red microcrystalline solid was collected, washed with methanol, and then diethyl ether. Yield: (65%).1_{H NMR (300 MHz,}

CD3OD): δ7.17 (t, 2H), 7.48 (d, 2H), 7.73 (m, 2H), 7.86 (m, 2H),

8.03 (d, 2H), 8.49 (m, 2H), 9.89 (s, 2H). Anal. Calcd for

Figure 1. Structures of salen ligands.

Table 1. Crystal Data and Structure Refinement Details for 6, 9, 11, and 12

6 9 11 12

formula C32H34F6N4O2PRu C22H22KN4O3Ru C26H20AuN6O2Ru C32H50Cl2N3O2Ru

Mr 752.67 530.61 746.52 680.72

cryst dimensions/mm 0.45× 0.08 × 0.06 0.19× 0.15 × 0.09 0.25× 0.10 × 0.04 0.27× 0.21 × 0.18

cryst syst tetragonal monoclinic orthorhombic monoclinic

space group P42/n P21/c Pbca P21/c

a/Å 21.166(3) 12.581(1) 13.2193(4) 11.817(3) b/Å 21.166(3) 16.369(2) 17.3094(5) 13.209(3) c/Å 14.369(3) 12.031(1) 21.5531(6) 22.033(4) β, deg 90 118.53(1) 90 97.762(19) V/ Å3 _6437.3(19) _2176.8(4) _4931.7(2) _3407.6(14) Z 8 4 8 4 F_calcd_{, mg m}-3 _1.553 _1.619 _2.011 _1.327 F(000) 3064 1076 2856 1428

no. of reflns. collected 7318 4891 4310 4456

no. of obsd reflns (I > 2σ(I)) 4167 3343 3325 2628

final R indices, I > 2σ(I) Ra _{R ) 0.0762, wR ) 0.2047} _{R ) 0.0329, wR ) 0.0674} _{R ) 0.0783, wR ) 0.1041} _{R ) 0.0572, wR ) 0.1574}

GOF 1.043 1.016 1.245 1.030

no. of parameters 394 281 327 314

Man et al.

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C21H18N3O7ClRu: C, 44.96; H, 3.21; N, 7.49. Found: C, 44.72; H,

3.11; N, 7.36. ESI-MS: m/z ) 430 (M+). Conductivity in CH3OH:

Λ) 87 Ω-1cm2_mol-1_.

Caution! Perchlorate salts are potentially explosiVe. Although we haVe not encountered any explosions so far, the amount of perchlorate salts used should be less than 100 mg each time.

[RuIII_(L2_)(NCCH

3)2][AuI(CN)2] (11). A mixture of 10a and

K[AuI_(CN)

2] in CH3OH/H2O (20 mL, 4:1 v/v) was stirred at 30

°C for 1 h. The deep-brown solution was concentrated to give a light-brown solid, which was recrystallized by slow evaporation of a solution in CH3CN/H2O (2:1 v/v). Yield (30%). IR (KBr,

cm-1): ν(CtN) 2140; ν(CdN) 1597. Anal. Calcd for C26H22

-N6O2AuRu: C, 41.82; H, 2.68; N, 11.26. Found: C, 42.02; H, 2.80;

N, 11.03. ESI-MS: m/z ) 498 (M+). [Nn_Bu

4][RuIII(L3)Cl2] (12). [NnBu4][RuVI(N)Cl4] (0.2 g, 0.4

mmol) was dissolved in THF (20 mL) and H2L3(0.108 g, 0.4 mmol)

was added. The solution was stirred at room temperature for 16 h and then evaporated to dryness. The resulting green residue was dissolved in CH2Cl2 and purified by column chromatography

(neutral alumina) with CH2Cl2as eluant. Dark-green crystals were

obtained by diffusion of diethyl ether into a concentrated CH2Cl2

solution of the solid. Yield: (45%). IR (KBr, cm-1): ν(CdN) 1601. Anal. Calcd for C32H50N3O2Cl2Ru · CH2Cl2: C, 51.77; H, 6.85; N,

5.49. Found: C, 51.92; H, 6.63; N, 5.49. ESI-MS: m/z ) 438 (M-). Conductivity in CH3CN: Λ ) 111 Ω-1cm2mol-1. µeff) 1.79 µB.

Kinetics. Kinetic experiments were done using either a Perki-nElmer Lamda 19 or a Hewlett-Packard 8452A diode-array UV-vis spectrophotometer. The ionic strengths of the solutions were maintained withn_Bu

4NPF6. The concentrations of py (4× 10-2to

3.0 M) were at least in 10-fold excess of that of 1 (1× 10-5to 5 × 10-5_{M). The reaction progress was monitored by observing the}

absorbance changes at 724 nm. Pseudo-first-order rate constants,

kobs, were obtained by nonlinear least-squares fits of Atversus time

t according to the equation At) A∞+ (A0- A∞) exp(-kobst), where

A0and A∞are the initial and final absorbances, respectively.

X-ray Crystallography. All measurements of 6, 9, 11, and 12 were made on either a Bruker Smart 1000 CCD or a Rigaku AFC7R diffractometer with graphite-monochromated Mo KR radiation (λ ) 0.71073 Å) in the ω-scan mode. Details of the intensity data collection and crystal data are given in Table 1. The data were corrected for Lorentz and polarization effects. Absorption correc-tions by the Ψ-scan method or an approximation by interimage scaling were applied. The structures were resolved by direct methods44_{and expanded using Fourier techniques.}45_All

calcula-tions were performed using the Crystal Structure or TeXsan crystallographic software package from Molecular Structure Cor-poration.46

Results and Discussion

Ligand-Induced N · · · N coupling of [RuVI_(N)(L1 )-(MeOH)]+(1). A solution of 1 in CH3CN (4.0× 10-5M) is stable for at least 24 h at room temperature. However, a very rapid spectral change occurs when excess pyridine (1.0

× 10-2_{M) is added; this is followed by a much slower step}

with isosbestic points at 323, 397, and 478 nm. The final spectrum is consistent with the quantitative formation of

[RuIII_(L1_)(py)2]+

(4). The formation of 4 follows clean pseudo-first-order kinetics; the pseudo-first-order rate

con-stant, kobs, is independent of [1] (1× 10-5to 5× 10-5M)

but depends linearly on [py]. At 298.0 K and I ) 0.05 M,

the second-order rate constant, k2, is (4.96 ( 0.12)× 10-1

M-1 s-1(Figure 2).

When higher concentrations of RuVI_{are used (>2}_{× 10}-2

M), gas bubbles of N2(GC/MS) can be observed upon adding

(44) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla, M.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.

(45) DIRDIF 99, Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; de Gelder, R.; Israel, R.; Smits, J. M. M. The DIRDIF-99 program system; Technical Report of the Crystallography Laboratory, University of Nijmegen: The Netherlands, 1999.

Table 2.UV-vis (CH3CN) and Electrochemical Data for 3-8 and 12

E1/2(Volts vs Cp2Fe+/0)a

complex λmax(nm(, M-1, cm-1)) RuIV/III RuIII/II

3 680 (4955), 497 (1940), 388 (17 540), 343sh (12 890), 234sh (44 590), 214 (49 270) 0.54 -0.89 4 723 (4650), 373 (16 490), 235 (43 650), 215 (41 510) 0.69 -0.58 5 734 (5015), 481 (1660), 332 (16 960), 232 (43 780) 0.89b _-0.30 6 705 (4880), 492 (1870), 363 (14 530), 346 (14 150), 233 (47 960), 202 (56 570) 0.58b _-0.86 7 670 (5920), 497 (2510), 387 (20 100), 366 (17 260), 234 (42 970), 217 (44 440) 0.57 -0.90 8 645 (5120), 514 (2395), 415 (21 930), 346 (11 850), 292 (8110), 238 (47 600), 221 (47 360) 0.10 -1.50b 12 647 (2360), 515 (1000), 415 (10 240), 347 (5880), 237 (24 400), 222 (25 000) 0.16 -1.39b

a_{Glassy carbon working electrode, platinum counter electrode, Ag/AgNO}

3reference electrode, 0.1 M [NnBu4]PF6in CH3CN as supporting electrode.

Ferrocene was added as internal standard.b_{Irreversible.}

Figure 2. Spectral changes at 180 s intervals for the reaction of 1 (4_× 10-5M) with py (0.01 M) in CH3CN at 298.0 K and I ) 0.05 M (a )

initial, b ) immediately after mixing using a two-compartment cell, c ) final). Inset shows the plot of kobsvs [py] for the second step (b f

c) [slope ) (4.96 ( 0.12)× 10-1; y intercept ) (5.81 ( 0.17)× 10-2; r ) 0.9986].

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excess pyridine. Using 15_{N labeling, it is shown that both}

nitrogen atoms in N2 come from RuVI

tN.41 These results

are consistent with the reaction scheme shown in eqs 6-9. The observed rapid first step is probably due to eqs 6 and 7, whereas the second step can be accounted for by eqs 8 and 9, with 8 being the rate-limiting step.

[RuVI(N)(L1)(NCCH)3]++ py h [RuVI(N)(L1)(py)]++

CH₃CN (6)

2[RuVI(N)(L1)(py)] +

f [(py)(L1)RuIIIN≡ NRuIII(L1)(py)]2+ (7)

[(py)(L1)RuIIIN≡ NRuIII(L1)(py)]2++

py f [RuIII(L1)(py)₂]++[RuIII(L1)(py)(N₂)]+(slow) (8)

[RuIII(L1)(py)(N2)]

+

+ py f [RuIII

(L1)(py)2]

+

+N2 (9)

In the pyridine-activated aziridination of alkenes by 1, there is kinetic evidence for the equilibrium described in eq

6, with K ) 15.6 M-1at 298 K.47 The [RuVI_(N)(L1_)(py)]+

species undergoes rapid N · · · N coupling to produce a µ-N2

RuIII_{species (eq 7). Rapid N · · · N coupling of [Os}V

(NH3)4-(N)]2+_{, generated from photolysis of [Os}VI_(NH3)4(N)]3+ _in

the presence of an electron donor, has been observed with k

) 3.75 × 105 _M-1 _s-1_.48

Because there should not be

significant π back bonding between N2 and RuIII_{, loss of}

bridging or terminal N2from RuIII_L1_{is expected to be facile}

(eqs 8 and 9). The y intercept of 5.81× 10-2s-1in the plot

of kobs versus [py] is probably due to a minor solvolysis

pathway shown in eq 10.

[(py)(L1)RuIIIN≡ N - RuIII(L1)(py)]2++

CH3CN f [Ru III (L1)(py)(NCCH3)] + +[RuIII (L1)(py)(N2)] + (10) The assumption that eq 8 is the rate-limiting step is valid if the coupling rate constant of eq 7 is similar to (or faster

than) that of [OsV_(NH3)4(N)]2+₍₄ _{× 10}5_M-1 _s-1_{). On the}

basis of the concentrations of 1 (4× 10-5M) and py (0.01

M) in the experiment, and the equilibrium constant of eq 6

(K ) 15.6 M-1), the equilibrium concentration of the adduct

is 6.2 × 10-6 M. If the coupling rate

constant of eq 7 is 4× 105_M-1_s-1_{, then the coupling rate}

in eq 7 is 1.6× 10-5M s-1at 298 K, which is around two

orders of magnetude faster than the observed rate 2× 10-7

M s-1 (which is assumed to be that of eq 8).

Attempts to detect the proposed [(py)(L1_)RuIII

NtNRuIII_(L1

)-(py)]2+_{intermediate by ESI-MS were unsuccessful. The mass}

spectrum (+ve mode) of (1) (4.0 × 10-5 M) and pyridine

(0.01 M) in CH3CN collected 5 min after mixing shows only

peaks due to [Ru(L)]+(m/z ) 422.1), [Ru(N)(L)]+(m/z )

436.2), [Ru(L)(NCCH3)]+(m/z ) 463.2), [Ru(L)(NCCH3)2]+

(m/z ) 504.3) and [Ru(L)(py)(NCCH3)]+(m/z ) 542.3).

The coordination of py onto RuVI

tN activates the complex

toward N · · · N coupling or attack by nucleophiles.41,47 A

similar activating effect by ligands has been observed in the

epoxidation of alkenes by [CrV_(salen)(O)]+

.6,49In the

pres-ence of ligands such as pyridine N-oxide (pyO), the

6-coordinate species [CrV_{(salen)(O)(pyO)]}+

is formed, which reacts much more rapidly with alkenes to give epoxide and

a (salen)CrIII_{product. X-ray crystallographic studies indicate}

that in the 5-coordinate [CrV_(salen)(O)]+

, the chromium atom is displaced 0.53 Å above the mean salen plane. However,

in the 6-coordinate [CrV_{(salen)(O)(pyO)]}+

, the chromium atom is pulled back to 0.26 Å. On the other hand, in

6-coordinate (salen)CrIII_{complexes such as [Cr(salen)(OH2)2]}+

, the chromium is only 0.077 Å displaced from the salen plane. Although the CrdO bond length increases by only 0.01 Å,

the ν(CrdO) stretch decreases from 1004 cm-1to 943 cm-1

upon ligation, indicating a weakening of the CrdO bond. Hence, upon coordination by a good donor ligand, the

CrV

dO species becomes more product-like, and this should lower the reorganization energy prior to oxygen atom

transfer. Similarly, in [RuVI_(N)(L1_)(MeOH)]+

the Ru atom

is displaced 0.39 Å from the mean L1_plane,41

whereas in a typical six-coordinate ruthenium(III) species such as

[RuIII_(L1_)(NH2Ph)2]+

, the ruthenium atom is only 0.075 Å

displaced from the L1 _{plane. Although we were unable to}

obtain the crystal structure or the IR spectrum of

due to its high reactivity, it is reasonable to assume that upon pyridine coordination, the ruthenium

atom is pulled back toward the L1_{plane and the RutN bond}

is weakened.

This facile ligand-induced N · · · N coupling reaction is utilized in the preparation of a series of new ruthenium(III) salen complexes, as described in the next section.

Synthesis of Ruthenium(III) Salen Complexes.

Treat-ment of [RuVI_(N)(L1_)(MeOH)]+

(1) with various ligands

affords a series of RuIII_L1_{complexes, as illustrated in Scheme}

2.

The diaquo species [RuIII_(L1_{)(OH2)2](PF6) (2), which is}

readily prepared from 1 by refluxing in water/acetone,43is

also a useful starting material for preparing various RuIII_L

complexes. 2-9 have room temperature magnetic moments

(solid sample, Gouy method) of µeff ) 1.86-2.07 µB,

consistent with their formulation as low-spin d5

ruthe-nium(III) complexes. Their UV-vis spectra in CH3CN (Table 2) display a broad band at 645-734 nm, which is

assigned to salen to a RuIII _{LMCT transition.}15

There are also intense peaks at 332-415 nm, which can be attributed to intraligand transitions of the coordinated salen ligand. The IR spectra of 2-9 display sharp ν(CdN) stretches at around

1600 cm-1. The IR spectrum of 5 shows a peak at 1017 cm-1,

which is absent in other RuIII_L1 _{complexes, and this is}

assigned to ν(SdO) stretch of S-bonded Me2SO. ν(SdO) stretch of S-bonded Ru-Me2SO complexes typically occur

(46) CrystalStructure, Single Crystal Structure Analysis Software, version 3.5.1; Rigaku/MSC Corporation: The Woodlands, Texas, USA, Rigaku, Akishima, Tokyo, Japan, 2003; Watkin, D. J. Prout. C. K., Carruthers. J. R., Betteridge, P. W. Crystals, Chemical Crystallography Lab: Oxford, UK, 1996; issue 10.

(47) Man, W. L.; Lam, W. W. Y.; Yiu, S. M.; Lau, T. C.; Peng, S. M. J. Am. Chem. Soc. 2004, 126, 15336–15337.

(48) Lam, H. W.; Che, C. M.; Wong, K. Y. J. Chem. Soc., Dalton Trans.

1992, 1411–1416. (49) Siddall, T. L.; Miyaura, N.; Huffman, J. C.; Kochi, J. K. J. Chem.Soc., Chem. Commun. 1983, 1185–1186. Man et al.

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at 1020-1134 cm-1, whereas that of O-bonded Ru-Me2SO complexes occur at lower wave numbers (885-954 cm-1).50–53 This assignment is also supported by electro-chemical studies (below). The ν(N-H) stretches for the

amines 6 and 7 occur at 3311, 3278 and 3300, 3244 cm-1

respectively. The ν(CtN) stretch at 2090 cm-1 for 9 is

similar to that of trans-[RuIII_{(acac)2(CN)2]}

-(2099 cm-1)54

and trans-[RuIII_{(salen)(CN)2]}

-(2080 cm-1).55

The ESI-MS of 2-9 in acetone exhibit a peak due to the parent ion (Experimental Section). For example, the ESI mass spectra of 3 (positive mode) and 8 (negative mode) (Figure 3) show one single peak that arises from the parent ion

[Ru(L1_)(1-MeIm)2]+_{(m/z ) 568) and [Ru(L}1_)Cl2]-_{(m/z )}

492), respectively.

(50) Reisner, E.; Arion, V. B.; Guedes da Silva, M. F. C.; Lichtenecker, R.; Eichinger, A.; Keppler, B. K.; Kukushkin, V. Y.; Pombeiro, A. J. L. Inorg. Chem. 2004, 43, 7083–7093.

(51) Alessio, E.; Mestroni, G.; Nardin, G.; Attia, W. M.; Calligaris, M.; Sava, G.; Zorzet, S. Inorg. Chem. 1988, 27, 4099–4106.

(52) Alessio, E.; Bolle, M.; Milani, B.; Mestroni, G.; Faleschini, P.; Geremia, S.; Calligaris, M. Inorg. Chem. 1995, 34, 4716–4721.

(53) Alessio, E.; Milani, B.; Bolle, M.; Mestroni, G.; Faleschini, P.; Todone, F.; Geremia, S.; Calligaris, M. Inorg. Chem. 1995, 34, 4722–4734.

(54) Yeung, W. F.; Man, W. L.; Wong, W. T.; Lau, T. C.; Gao, S. Angew.

Chem., Int. Ed. 2001, 40, 3031–3033. (55) Yeung, W. F.; Lau, P. H.; Lau, T. C.; Wei, H. Y.; Sun, H. L.; Gao,S.; Chen, Z. D.; Wong, W. T. Inorg. Chem. 2005, 44, 6579–6590. Scheme 2. Synthesis of RuIII_L1_{Complexes via Ligand-Induced N · · · N Coupling of the Corresponding Ruthenium(VI) Nitride}

Figure 3. ESI mass spectra of 3 in the positive mode (left) and 8 in the negative mode (right) in acetone. Insets show the experimental (top) and calculated (bottom) isotopic patterns.

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The cyclic voltammograms of 3-8 in CH3CN (Table 2)

exhibit two reversible couples, which are assigned to RuIV/III

and RuIII/II_{couples, except for 5 and 6 where the oxidation}

waves are irreversible (Figure 4). As expected, compounds

with anionic axial ligands (8, 12) have lower RuIV/III _and

RuIII/II_{potentials. For a compound with neutral axial ligands,}

the RuIII/II_{potential increases with the π-accepting ability of}

the ligand. 5 has the highest RuIII/II_{potential, consistent with}

evidence from IR that the Me2SO ligands are S-bonded; S-bonded Me2SO is a strong π-acceptor ligand that would

stabilize RuII_{, whereas the O-bonded ligand would have little}

π-accepting ability.56

The molecular structures of 6 (Figure 5) and 9 (Figure 6) have been determined by single-crystal X-ray diffraction method. The crystal data and structural refinement details are given in Table 1. Selected bond distances and angles are listed in Table 3 and 4. 6 and 9 adopt a distorted octahedral geometry; the ruthenium center is bonded to the

two oxygen atoms and the two nitrogen atoms of the L1

ligand in the equatorial plane. They have similar Ru-O bond distances (2.027(4) and 2.029(4) Å for 6, 2.018(2) and 2.022(2) Å for 9) and Ru-N bond distances (1.986(5) and 1.982(6) Å for 6, (1.996(2) and 1.993(2) Å for 9). 6 is the first crystal structure of a ruthenium(III) complex of PhNH2.

Its Ru-Nanilinebond distances of 2.126(5) and 2.141(12) Å

are slightly shorter than that of the ruthenium(II) species

[RuII_{(NH2Ph){PhNC(H)NPh}(Me2SO)2Cl] (2.1907(19) Å).}57

In 9, the Ru-Ccyanidebond distances (2.067(4) and 2.075(4)

Å) are similar to that in (Nn_Bu4)[RuIII_{(salen)(CN)2] (2.04(2)}

and 2.09(2) Å).55

We have previously used [Au(CN)2]-as a bridging ligand

for the construction of coordination polymers.58,59Our initial

goal in this study was to use [Au(CN)2]-as a ligand to induce

N · · · N coupling, which may result in the formation of a

polynuclear species. However, treatment of [RuVI_(N)(L2_)Cl]

with K[Au(CN)2] in CH3OH/H2O did not result in the

coordination of [Au(CN)2]- onto ruthenium, instead

[RuIII_(L2_{)(NCCH3)2][Au(CN)2] (11) was isolated after}

re-(56) Wishart, J. F.; Taube, H.; Breslauer, K. J.; Isied, S. S. Inorg. Chem. 1984, 23, 2997–3001.

(57) Clark, T.; Cochrane, J.; Colson, S. F.; Malik, K. Z.; Robinson, S. D.; Steed, J. W. Polyhedron 2001, 20, 1875–1880.

(58) Yeung, W. F.; Wong, W. T.; Zuo, J. L.; Lau, T. C. J. Chem. Soc., Dalton Trans. 2000, 629–631.

(59) Shek, I. P. Y.; Wong, W. Y.; Lau, T. C. New J. Chem. 2000, 24, 733–734.

(60) Demerseman, B.; Renaud, J. L.; Toupet, L.; Hubert, C.; Bruneau, C. Eur. J. Inorg. Chem. 2006, 7, 1371–1380.

Figure 4. Cyclic voltammograms of 3 (a), 6 (b), and 7 (c) in CH3CN.

Figure 5. ORTEP diagram of [RuIII_(L1_)(NH

2Ph)2]+ cation (6); thermal

ellipsoids are drawn at 30% probability (hydrogen atoms are omitted except N(3)-H and N(4)-H for clarity).

Figure 6. ORTEP diagram of [RuIII_(L1_)(CN)

2]-anion (9), thermal ellipsoids

are drawn at 30% probability (hydrogen atoms are omitted for clarity). Table 3. Selected Bond Distances (Angstroms) and Angles (Degrees) of 6 Ru(1)-O(1) 2.029(5) Ru(1)-N(3) 2.126(5) Ru(1)-O(2) 2.027(4) Ru(1)-N(4) 2.141(12) Ru(1)-N(1) 1.986(5) N(1)-C(7) 1.291(9) Ru(1)-N(2) 1.982(6) N(2)-C(14) 1.287(9) O(1)-Ru(1)-O(2) 91.25(17) N(1)-Ru(1)-N(2) 83.3(2) O(1)-Ru(1)-N(1) 92.8(2) N(1)-Ru(1)-N(3) 94.3(2) O(1)-Ru(1)-N(2) 176.0(2) N(1)-Ru(1)-N(4) 89.4(6) O(1)-Ru(1)-N(3) 86.6(2) N(2)-Ru(1)-N(3) 94.8(2) O(1)-Ru(1)-N(4) 92.7(7) N(2)-Ru(1)-N(4) 86.2(7) O(2)-Ru(1)-N(1) 175.9(2) N(3)-Ru(1)-N(4) 176.3(5) O(2)-Ru(1)-N(2) 92.6(2) Ru(1)-N(1)-C(7) 125.9(5) O(2)-Ru(1)-N(3) 86.7(2) Ru(1)-N(2)-C(14) 126.1(5) O(2)-Ru(1)-N(4) 89.7(6)

Table 4.Selected Bond Distances (Angstroms) and Angles (Degrees) of 9 Ru(1)-O(1) 2.018(2) Ru(1)-C(22) 2.067(4) Ru(1)-O(2) 2.022(2) N(1)-C(7) 1.286(4) Ru(1)-N(1) 1.996(2) N(2)-C(14) 1.290(4) Ru(1)-N(2) 1.993(2) C(21)-N(3) 1.157(4) Ru(1)-C(21) 2.076(4) C(22)-N(4) 1.147(4) O(1)-Ru(1)-O(2) 91.82(8) N(1)-Ru(1)-N(2) 83.28(10) O(1)-Ru(1)-N(1) 92.67(9) N(1)-Ru(1)-C(21) 94.77(4) O(1)-Ru(1)-N(2) 175.56(9) N(1)-Ru(1)-C(22) 88.55(11) O(1)-Ru(1)-C(21) 92.93(11) N(2)-Ru(1)-C(21) 85.63(12) O(1)-Ru(1)-C(22) 90.56(11) N(2)-Ru(1)-C(22) 91.15(12) O(2)-Ru(1)-N(1) 174.90(9) C(21)-Ru(1)-C(22) 175.07(13) O(2)-Ru(1)-N(2) 92.31(9) Ru(1)-N(1)-C(7) 124.9(2) O(2)-Ru(1)-C(21) 87.40(11) Ru(1)-N(2)-C(14) 124.8(2) O(2)-Ru(1)-C(22) 89.00(11) Man et al.

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crystallization from CH3CN/H2O. It shows a peak at 2140

cm-1in the IR, which is assigned to the ν(CtN) stretch of

[Au(CN)2]-. The [Au(CN)2]-functions only as a counterion,

in fact [RuIII_(L2_{)(NCCH3)2]PF6}_{can be obtained by refluxing}

[RuVI_(N)(L2_{)(CH3OH)](ClO4) in CH3CN. In both compounds}

the ν(CtN) stretch of the coordinated CH3CN is too weak to be observed. The X-ray crystal structure of 11 is shown in Figure 7, and the details of the crystal data and selected bond data are listed in Tables 1 and 5, respectively. The two CH3CN ligands are trans with a N(3)-Ru-N(4) angle of

175.9(4)°. The two Ru-Nacetonitrilebond distances are identical

(2.040(9) and 2.041 (9) Å), and are comparable to that of

[RuII_{(Cp*)(Ph2POMe)(NCCH3)2] (2.067(2) and 2.076(2) Å)}60

and mer-[RuIII_{(NCCH3)3Cl3] (2.014(7)-2.065(7) Å).}61

Attempts to prepare a ruthenium(VI) nitrido complex of

the parent salen ligand by a reaction of [Nn_Bu4][RuVI_(N)Cl4]

with H2L3was unsuccessful; instead the dark-green complex

[Nn_Bu4][RuIII_(L3_{)Cl2] (12) was obtained. 12 has a}

room-temperature magnetic moment of µeff ) 1.79 µB (solid

sample, Gouy method) consistent with its formulation as a

low-spin d5 _RuIII _{complex. The ESI mass spectrum (-ve}

mode) of 12 in acetone shows a single peak at m/z ) 438,

which is assigned to the parent ion [RuIII_(L3_)Cl2]-_{. The cyclic}

voltammogram of 12 (Figure 8) in CH3CN shows a reversible

oxidation wave at E1/2 ) +0.16 V (vs Cp2Fe+/0) and an

irreversible reduction wave at Epa) -1.39 V (vs Cp2Fe+/0),

which are assigned to RuIV/III_{and Ru}III/II_{couples, respectively.}

The potentials are comparable to that of 8 (Table 2). The

irreversibility of the RuIII/II _{couple may be due to chloride}

dissociation in the RuII _state.

Single crystals suitable for X-ray crystallography were obtained by slow diffusion of diethyl ether into a CH2Cl2 solution of 12. The molecular structure of the anion is shown in Figure 9. Crystal data, structural refinement details, and selected bond distances and angles are given in Tables 1 and 6. The two chlorine atoms are trans with a Cl(1)-Ru-Cl(2)

angle of 179.22(10)°. The two Ru-Cl bond distances are

identical (2.386(2) and 2.378(2) Å) and are comparable to those in trans-PPh4[Ru(acac)2Cl2] (2.355(2) and 2.362(1)

Å).62

Conclusions

Ruthenium(VI) nitrido complexes bearing salen-type ligands readily undergo facile ligand-induced N · · · N coupling

reac-(61) Appelbaum, L.; Heinrichs, C.; Demtschuk, J.; Michman, M.; Oron, M.; Schafer, H. J.; Schumann, H. J. Organomet. Chem. 1999, 592, 240–250.

(62) Hasegawa, T.; Lau, T. C.; Taube, H.; Schaefer, W. P. Inorg. Chem. 1991, 30, 2921–2928.

Figure 7. ORTEP diagram of [RuIII_(L2_)(NCCH

3)2]+cation (11), thermal

ellipsoids are drawn at 30% probability (hydrogen atoms are omitted for clarity).

Table 5.Selected Bond Distances (Angstroms) and Angles (Degrees) of 11 Ru(1)-O(1) 2.011(6) Ru(1)-N(4) 2.040(9) Ru(1)-O(2) 2.002(6) N(1)-C(7) 1.305(13) Ru(1)-N(1) 1.992(8) N(2)-C(14) 1.297(12) Ru(1)-N(2) 2.016(8) N(3)-C(21) 1.145(13) Ru(1)-N(3) 2.041(9) N(4)-C(22) 1.111(15) O(1)-Ru(1)-O(2) 90.4(3) N(1)-Ru(1)-N(2) 82.4(3) O(1)-Ru(1)-N(1) 93.8(3) N(1)-Ru(1)-N(3) 88.0(4) O(1)-Ru(1)-N(2) 175.9(3) N(1)-Ru(1)-N(4) 89.8(4) O(1)-Ru(1)-N(3) 88.6(3) N(2)-Ru(1)-N(3) 92.8(4) O(1)-Ru(1)-N(4) 88.1(4) N(2)-Ru(1)-N(4) 90.4(4) O(2)-Ru(1)-N(1) 175.4(3) N(3)-Ru(1)-N(4) 175.9(4) O(2)-Ru(1)-N(2) 93.5(3) Ru(1)-N(3)-C(21) 177.1(9) O(2)-Ru(1)-N(3) 90.2(4) Ru(1)-N(4)-C(23) 169.6(11) O(2)-Ru(1)-N(4) 92.2(4)

Figure 8. Cyclic voltammogram of 12 in CH3CN.

Figure 9. ORTEP diagram of [RuIII_(L3_)Cl

2]-anion (12), thermal ellipsoids

are drawn at 30% probability (hydrogen atoms are omitted for clarity). Table 6.Selected Bond Distances (Angstroms) and Angles (Degrees) of 12 Ru(1)-O(1) 2.029(6) Ru(1)-Cl(1) 2.386(2) Ru(1)-O(2) 2.040(6) Ru(1)-Cl(2) 2.378(2) Ru(1)-N(1) 1.984(7) N(1)-C(3) 1.283(11) Ru(1)-N(2) 1.992(8) N(2)-C(16) 1.270(12) O(1)-Ru(1)-O(2) 91.9(2) O(2)-Ru(1)-Cl(2) 89.18(18) O(1)-Ru(1)-N(1) 92.2(3) N(1)-Ru(1)-N(2) 83.8(4) O(1)-Ru(1)-N(2) 175.9(3) N(1)-Ru(1)-Cl(1) 88.2(2) O(1)-Ru(1)-Cl(1) 89.66(19) N(1)-Ru(1)-Cl(2) 91.7(2) O(1)-Ru(1)-Cl(2) 91.12(19) N(2)-Ru(1)-Cl(1) 90.4(2) O(2)-Ru(1)-N(1) 175.8(3) N(2)-Ru(1)-Cl(2) 88.8(2) O(2)-Ru(1)-N(2) 92.2(3) Cl(1)-Ru(1)-Cl(2) 179.22(10) O(2)-Ru(1)-Cl(1) 90.83(18)

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tions, which provide a general synthetic pathway for a variety of (salen)ruthenium(III) complexes. Our studies should greatly increase the scope for the application of ruthenium salen complexes as catalysts for various organic transforma-tions. The catalytic properties of some of these complexes will be investigated.

Acknowledgment. The work described in this article was supported by the Research Grants Council of Hong Kong

(CityU 2/06C, CityU 101404) and the City University of Hong Kong (7001799).

Supporting Information Available: UV-vis spectra of 3-9 and the ESI-MS of reaction of (1) and py in CH3CN taken in 5

min. This material is available free of charge via the Internet at http://pubs.acs.org.

IC800263N

Man et al.