Inorganica Chimica Acta 342 (2003) 125 /130 www.elsevier.

com/locate/ica

Cyclic voltammetry of metal complexes of nitrones and nitroxides

Frederick A. Villamena 1, Vaclav Horak, DeLanson R. Crist 1
Department of Chemistry, Georgetown University, Washington, DC 20057-2222, USA Received 6 February 2002; accepted 17 June 2002

Abstract Increasing interest in radicals bound to metals led to the present study of electron transfer to and from metal nitrone complexes and metal nitroxides. These are species involved in biological spin trapping and materials science applications, respectively. Cyclic voltammetry was used to study the redox behavior of complexes of the bidentate N -tert -butyl-a-(2-pyridyl)nitrone (2-PyBN) and the monodentate nitrone 2,5,5-trimethyl-1-pyrroline-N -oxide (M3PO) with metal hexafluoroacetylacetonates M(hfac)2 in CH2Cl2. Bidentate complexes M(2-PyBN)(hfac)2 with M 0/MnII and CoII were easier to oxidize in CH2Cl2 (less positive Epa) than the corresponding M(hfac)2 and harder to reduce (more negative Epc). In MeCN, this behavior was also observed for M0/CoII and NiII which indicate more facile oxidation when M3PO is present as co-ligand compared with M(hfac)2 alone. CVs of M(2-PyBN)(hfac)2 and [M(M3PO)(hfac)2]2 in MeCN gave common reduction peaks due to hfac. Nitroxides (aminoxyls) 2,2,6,6-tetramethylpiperidine1-oxyl (TEMPO) and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-oxyl (CPNO) gave quasi-reversible oxidations to oxoammonium cations, while N -tert -butyl-(2-pyridyl)phenylmethanaminoxyl (2-PyBNO) showed only irreversible oxidations. CV of solutions of CPNO in the presence of M(hfac)2, where M is MnII, CoII, or NiII, indicated formation of metal /nitroxide complexes for CoII and NiII. For stable metal nitroxides prepared independently, the CV of Mn(TEMPO)2 (hfac)2 showed dissociation to free nitroxide and Mn(hfac)2 in CH2Cl2, while M(2-PyBNO)(hfac)2 gave distinctive CVs for M0/MnII, CoII, and NiII. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nitrones; Nitroxides; Hexauoroacetylacetonate metal complexes; Cyclic voltammetry

1. Introduction Since many applications of nitrones, such as their use in synthesis [1] and spin trapping, [2] may involve metal ions as catalysts, an extensive X-ray structural study of metal nitrone complexes was recently carried out [3]. Reactions of these complexes with phenyl radical was studied, [4] and in some cases metal nitroxides (aminoxyls) were identified as products. This spin trapping is shown below (Fig. 1) for a metal hexafluoroacetylacetonate M(hfac)2 complex with N -tert -butyl-a-(2-pyridyl)nitrone (2-PyBN). In general, the interaction of metals with nitroxides is important because metals may be present when nitroxides are formed from radical precursors or in biological systems when nitroxides are used as biophysical

1 Corresponding authors E-mail address: villamef@georgetown.edu (F.A. Villamena).

probes [5]. Also, some metal nitroxides may have potential applications as molecular magnets [6]. A reaction of a stable nitroxide with FeII was described, [7a] and a recent study to understand the anti-oxidant activity of stable nitroxides was carried out with FeII under physiological conditions [7b]. However, the redox behavior of metal nitroxide complexes by CV has not been reported. Electrochemical studies of uncomplexed nitrones [8,9] and nitroxides, [10] on the other hand, were described several years ago. Nitrones relevant to the present work, N -tert -butyl-a-(phenyl)nitrone (PBN), 2-PyBN, and 2,2-dimethyl-1-pyrroline-1-oxide (DMPO), underwent irreversible one-electron oxidations [8]. CV of the nitroxide 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives provided insights into mechanisms and kinetics of their redox reactions, [10a] and a recent study showed that their oxidation potentials correlate with catalytic efficiency for oxidation of alcohols [11]. Anodic oxidation of nitroxides to oxoammonium cations (Fig. 2) are generally quasi-reversible in

0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 1 1 5 4 - 4

126

F.A. Villamena et al. / Inorganica Chimica Acta 342 (2003) 125 /130

Fig. 1. Phenyl radical trapping of M(2-PyBN)(hfac)2.

non-aqueous solvents, and the Epa of saturated heterocyclic nitroxides depend on ring size and substituents [10c,12]. Such nitroxides owe their long lifetimes primarily to thermodynamic stability (N /O delocalization energy of /32 kcal mol (1), [13] as well as kinetic stability (steric hindrance to attack). Also, the absence of hydrogen on the a carbon prevents disproportionation reactions [13]. Another frequently used nitroxide with these structural features is 3-carbamoyl-2,2,5,5tetramethyl-3-pyrroline-1-oxyl (CPNO). We now report exploratory CV results for metal complexes of 2-PyBN and the monodentate 2,5,5trimethyl-1-pyrroline-N -oxide (M3PO) as compared with the free ligands. Molecular weight studies showed that all complexes exist predominately as molecular monomers in CH2Cl2, except for M(M3PO)(hfac)2 which is dimeric for MnII and a mixture of monomers and dimers for CoII and NiII [4]. Also investigated by CV was the effect of MnII, CoII, and NiII complexation on the redox behavior of nitroxides TEMPO, CPNO, and 2-PyBNO (Fig. 3).

2. Experimental Cyclic voltammetry was done on a Cypress Systems Model CS-1090 potentiostat and computer-controlled electroanalytical system and, for experiments with CPNO, on a BAS100B system. Electrochemical measurements were carried out in a 5 ml cell equipped with a glassy-carbon working electrode (BAS, 0.09 cm2), platinum-wire auxiliary electrode, and a Ag/AgNO3 refer-

ence electrode filled with 0.01 M AgNO3 and 0.1 M tetraethylammonium perchlorate (TEAP) in acetonitrile. The glassy carbon electrode was cleaned before each run by rubbing (circular motion for approximately 10 s) on a polishing pad with wet, 0.05 micron, gamma alumina and then washed with water /acetone. Solutions were degassed by bubbling with nitrogen through a stirred solution. Background current (solvent with supporting electrolyte) corrections were done for all measurements. Acetonitrile (MeCN) and methylene chloride (CH2Cl2) solvents (Fischer Scientific, 99.9% HPLC grade) were used without further purification. TEAP, tetrabutylammonium hexafluorophosphate (Aldrich), ferrocene (Aldrich), 2,2,6,6-tetramethylpiperidine-1oxyl (TEMPO) (Acros), 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-oxyl (CPNO) (Aldrich), and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Aldrich) were used as purchased. Alumina (Micropolish B) was obtained from Buehler. Preparation of 2-PyBN and M3PO and their complexes was described previously [3] as well as 2-PyBNO and its complexes [19] and Mn(TEMPO)2 (hfac)2 [18]. CVs were taken on 3 mM solutions except for the dimeric [3] [M(2-PyBN)2(hfac)][M(hfac)3] and [M(M3PO)(hfac)2]2 with M 0/MnII, CoII, and NiII which were 1.5 and for 6 mM CPNO in the presence of 3.0 mM M(hfac)2. All solutions contained 0.1 M TEAP unless otherwise stated. A ferrocene standard showed Epa (ferrocene/ferricinium) at 0.22 V in acetonitrile and 0.37 in methylene chloride. Voltage was cycled between (/2.0 and 2.0 V beginning at (/2.0 V at a scan rate of 100 mV s (1 unless otherwise stated.

Fig. 2. Reversible redox property of TEMPO (left) and structure of CPNO (right).

Fig. 3. Structure of M3PO and 2-PyBNO.

F.A. Villamena et al. / Inorganica Chimica Acta 342 (2003) 125 /130 Table 1 Redox potentials of M(hfac)2 in the presence and absence of nitrones in acetonitrile and methylene chloride Epa
b

127

Epc Second oxidation

First oxidation Ligands 2-PyBN hfac(1 c Hhfac d M3PO M(hfac)2 Mn Fe Co Ni Cu Zn M(2 -PyBN)(hfac)2 Mn Fe Co Ni Cu Zn M(M3 PO)(hfac)2 Mn Co Ni
a b c d e f g g g

First reduction

Second reduction

1.38(1.47) 1.09 (0.97 1.17(1.28) 1.28(1.34) 0.91(0.52) 1.86(! 2.00) 0.28 f(1.68) e (0.32((0.14) ! 2.00(! 2.00) 1.28(1.27) 0.52(0.61) 1.50(1.41) 1.79(1.8) (0.39((0.07) 2.00(! 2.00) 1.23(1.24) 1.19(1.43) 1.18(1.36) 1.56(1.85) 1.14 (1.52(1.4) 0.50(0.39) (1.44((0.85) (1.58((0.97) (0.30(0.16) (1.39((1.64) (1.46((1.35) 0.46(0.39) (1.47((1.60) (1.50((1.72) (0.14((0.37) (1.72 (1.76((1.80) (1.64 (1.66 (0.82 (1.73((1.88) (1.65 (1.50((1.71) (1.62 (0.88((0.80) (1.50 (1.85 (1.64((1.85) (1.66((1.49)

e e

0.85(0.77)

1.58 0.67

1.54(1.31)

(1.56 (1.43((1.48) (1.55((1.36)

Values for CH2Cl2 in parenthesis. All measurements were carried out in 3 mM solutions with 0.1 M TEAP unless otherwise noted. Peak potentials relative in V to Ag/0.01 M AgNO3 with 100 mV s (1 scan rate. From 1 equiv. Bu4NOH'1 equiv. 1,1,1,5,5,5-hexafluoro-2,4-pentanedione. 1,1,1,5,5,5-Hexafluoro-2,4-pentanedione. With 0.1 M tetrabutylammonium hexafluorophosphate. Lower peak current than other M(hfac)2 peaks. Introduced in solution as independently prepared and isolated metal complexes with stoichiometry of 1:1 M(hfac)2:nitrone.

3. Results and discussion Cyclic voltammograms exhibited irreversible oxidations for 2-PyBN, M3PO, and hfac (1 ligands and an irreversible reduction for the neutral diketone Hhfac (see Table 1 for peak potentials). As a general observation for M(hfac)2 and M(2-PyBN)(hfac)2, scanning from (/2.0 to 2.0 V and then back gave cathodic peaks in the (/2.0 to 0 V range that increased significantly from the first scan (B/20:A) to the second scan (50 /100:A) and resembled reduction of a species immobilized on the surface. Oxidation of Zn(hfac)2 and Zn(2-PyBN)(hfac)2 did not occur prior to solvent breakdown, while only small reduction peaks were observed between 1.39 and (/1.50 V. 3.1. Bidentate nitrone complexes Solution studies such as conductivity and vapor pressure osmometry of M(2-PyBN)(hfac)2 in CH2Cl2 showed formation of neutral molecular species from those that existed as complex salts in the solid state [4].

Moreover, 1H NMR [4] and UV /Vis /Near-IR3 spectra indicates octahedral and high spin forms exist in solution ruling out the possibility that a square-planar and low-spin complexes are formed in solution. This result establishes the initial structures for the complexes before electrochemical reactions were carried out. The oxidation peak potentials for each M(2-PyBN)(hfac)2 are different from either 2-PyBN or the M(hfac)2 as seen in Table 1. These values, therefore, are characteristic of the complexes and may also represent partially dissociated species. Reduction potentials for most M(2-PyBN)(hfac)2 were more negative compared with their corresponding M(hfac)2. Shifts to more negative reduction potentials for M(2-PyBN)(hfac)2 relative to M(hfac)2 were observed for the first reduction peaks of MnII (1.45), CoII (0.81), NiII (0.75), and CuII (0.53 V). Polarographic studies on various CuII, [14] RuIII, [15] and CrIII [16] 1,3diketonato complexes showed that substituting electrondonating groups for hydrogen on the ligand makes E1/2 reduction potentials more negative, and conversely for electron-attracting groups. Therefore, shifts to more

128

F.A. Villamena et al. / Inorganica Chimica Acta 342 (2003) 125 /130 Table 2 Peak potentials of M(hfac)2 in the presence of equimolar or excess nitroxides a Epa TEMPO Mn(TEMPO)2(hfac)2 CPNO CPNO /Mn c CPNO /Co c CPNO /Ni c 2-PyBNO Mn(2-PyBNO)(hfac)2 d Co(2-PyBNO)(hfac)2 d Ni(2-PyBNO)(hfac)2 d
a b

negative reduction potentials for most of 2-PyBN complexes relative to the corresponding M(hfac)2 lead to the conclusion that 2-PyBN acts as an electron donor. The M(2-PyBN)(hfac)2 for M 0/FeII, CuII and NiII gave oxidation potentials higher than their corresponding M(hfac)2. However, for M(2-PyBN)(hfac)2 for M 0/ MnII and CoII, less positive oxidation potentials than their M(hfac)2 analogues were observed with the following Epa shifts (in volts): MnII, 0.07 and CoII, 0.59. These shifts to less positive oxidation potentials which are more pronounced in CoII than MnII indicate a more favorable oxidation when 2-PyBN is a co-ligand, and that MnII is more dissociated in solution. One explanation for easier oxidation of M(2PyBN)(hfac)2 relative to M(hfac)2 is an electron-donating effect of 2-PyBN in mixed-ligand complexes. However, this would be a constant factor for all complexes. Differences in Epa shifts for the various metals suggest an additional factor that is metal-specific. Sawyer [17] has rationalized that a shift to less positive oxidation potential for metal complexes is due to stabilization resulting from formation of a covalent bond involving an unpaired d electron of the metal and an unpaired p electron of the ligand. However, it should be noted that this rationale does not necessarily suggest the formation of a covalent-bond in M(2-PyBN)(hfac)2 during redox process. Different Epa shifts for M-2-PyBN may, therefore, be accounted for by the electron-donating ability of 2-PyBN and a metal-specific stabilization. Although we do not know the nature of M(2PyBN)(hfac)2 in MeCN, their CVs in MeCN were nevertheless taken. The oxidation potentials for most of M(2-PyBN)(hfac)2 (except for M 0/NiII) show a less positive oxidation potential compared with M(hfac)2 consistent with the previous observations from some complexes in CH2Cl2. Interestingly, reduction potential for M(2-PyBN)(hfac)2 near (/1.4/(/1.5 V and the second peaks near (/1.6/(/1.7 V indicate similarities of their electrochemistry with M(hfac)2 and may suggest a common decomposition product due mainly to the hfac ligand in both types of complexes. 3.2. Monodentate nitrone complexes Structures of M(M3PO)(hfac)2 in CH2Cl2 were reported to be dimeric except for MnII which was found to be partly dissociated. The oxidation potential of M3PO is different to those observed for M(M3PO)(hfac)2. Oxidation potentials of M(M3PO)(hfac) for M 0/CoII and NiII are less positive than their M(hfac)2 counterparts while reduction potentials are more negative. Characteristic Epa of 1.43 V for Co(M3PO)(hfac)2 and 1.36 V for Ni(M3PO)(hfac)2 were observed, compared with Epa !/2.0 V for Co(hfac)2 and 1.68 V for Ni(hfac)2. These shifts to less positive potentials on complexation with M3PO, which are metal specific (!/0.57 V for CoII

Epc

0.68 0.65, 0.83, 0.81, (0.12, 0.82, 0.69, 1.14, 1.40, 1.47,

1.40, 1.73 1.70 1.45 0.87, 1.38 1.72 1.51 1.46 1.80 1.80

0.34 0.32 0.55 1.35, 0.55 1.38, 0.46, (0.52 0.54, (0.40, (0.60 1.26, 0.88, (0.90 (1.03 (1.09

All CV for 3 mM solutions in CH2Cl2 with 0.1 M tetrabutylammonium hexafluorophosphate unless otherwise stated. Data restricted to the (1.1 to 2.0 V range. b Peak potentials in V relative to Ag/0.01 M AgNO3 with 100 mV s (1 scan rate. c Solutions 3 mM in M(hfac)2 and 6 mM in CPNO. d Introduced in solution as independently prepared and isolated metal complexes with stoichiometry of 1:1 M(hfac)2:2-PyBNO. Table 3 Values of Ep/2, DEp, and current ratios for nitroxide /oxoammonium couples a Ep/2 TEMPO Mn(TEMPO)2(hfac)2 CPNO CPNO /Mn c CPNO /Co c CPNO /Ni c 0.51 0.48 0.69 0.68 0.66 0.68
b

DEp 0.34 0.33 0.28 0.26 0.41 0.28

irc/ira 1.0 0.9 1.0 1.2 1.5 1.5

a From CV in CH2Cl2 containing 0.1 M tetrabutylammonium hexafluorophosphate with potentials in V relative to Ag/Ag ' and 100 mV s (1 scan rate. b Ep/2 0 1/2(Epa'Epc). c Solutions 3 mM in M(hfac)2 and 6 mM in CPNO.

and 0. 32 V for NiII), suggest electron donation by the nitrone and metal stabilization of the oxidized species, as proposed for M(2-PyBN)(hfac)2. In MeCN, almost the same oxidation potentials were observed for the three M(M3PO)(hfac)2, with M 0/MnII (1.23 V), CoII (1.19 V), and NiII (1.18 V). Since oxidation of M3PO occurs at 1.17 V, the similarity of all Epa values suggests that these correspond to oxidation of dissociated M3PO in MeCN. The M(M3PO)(hfac)2 also gave Epc values that are the same for the reduction of the corresponding M(hfac)2, indicating complete dissociation of M(M3PO)(hfac)2 to M3PO and solvated M(hfac)2. 3.3. Nitroxides and their complexes TEMPO exhibits a quasi-reversible, one-electron oxidation in MeCN with ipc/ipa 0/1.0 and Ep 0/0.09 V.

F.A. Villamena et al. / Inorganica Chimica Acta 342 (2003) 125 /130

129

Scheme 1. Possible mechanisms of 2-PyBNO decomposition after oxidation.

The value of Ep/2 0/1/2(Epa'/Epc) for this couple is 0.40 which compares reasonably well with a reported value of 0.322 in the same medium [10a]. However, to minimize dissociation problems, CVs were taken in CH2Cl2. In this solvent Ep was 0.34 V (Table 2) and the ip,c/ip,a current ratio remained 1.0 (Table 3). Mn(TEMPO)2(hfac)2, prepared in crystalline form, [18] apparently dissociates even in CH2Cl2, since the observed quasi-reversible couple with Epa 0/0.65 V and another Ep,a of 1.40 V (see Table 2) correspond to TEMPO and Mn(hfac)2, respectively. The CV of CPNO also shows a quasi-reversible oxidation and peak potentials (Table 2) consistent with literature values [10c] and a similar degree of irreversibility by the criteria in Table 3. The Ep/2 of that redox couple stayed the same when Mn(hfac)2 was added, and peaks for free Mn(hfac)2 were observed at 1.45 and 1.35 V (Table 2). This behavior is consistent with no complex formation for MnII in CH2Cl2. However, when Co(hfac)2 or Ni(hfac)2 was added to a CPNO solution, new peaks not present in either CPNO or M(hfac)2 appeared, suggesting the presence of the metal /nitroxide complex. These new peaks (Table 2) are, therefore, characteristic for the undissociated complexes. For the Co complex, these peaks were at 1.38, 0.52 and (/0.12 V, and for the Ni complex at 0.40 and (/0.60 V. The presence of some free CPNO in all cases was indicated by peaks for a quasi-reversible redox system with Ep/2 values corresponding to the CPNO /oxoammonium couple (Table 3). Nitroxide 2-PyBNO, prepared [19] by AgI oxidation of the corresponding hydroxylamine, however, does not show the characteristic quasi-reversible oxidation sys-

Table 4 Oxidation potentials for selected ligands Ligand Pyridine 2-PyBN M3PO hfac ( CPNO 2-PyBNO TEMPO
a b

Epa 2.23 1.38 1.17 1.09 0.83 0.69 0.68

a b c c c d d d

In V relative to Ag/0.01 M AgNO3 with 100 mV s (1 scan rate. In MeCN, from the value of 2.30 vs. SCE taken from ref. [8] and adjusted to a Ag/Ag ' reference electrode. c In MeCN. d In CH2Cl2.

tem found for TEMPO and CPNO. Anodic peaks at 0.69 and 1.51 V (Table 2) almost completely disappeared on the second scan, presumably due to fouling of the electrode surface. No corresponding Epc were observed on reverse scans as evidence of irreversibility. The similarity of Epa for the first oxidation peak to those of TEMPO and CPNO suggests that the 0.69 V peak corresponds to oxidation of the nitroxide group. Irreversibility in the case of 2-PyBNO may be due to the presence of a hydrogen on the a carbon or of a tert butyl group on nitrogen. Elimination of either H or tert butyl may lead to fast decomposition of the oxoammonium ion (see Scheme 1). Lack of reversibility may also be due to the presence of an a-phenyl group [11]. Complexes of 2-PyBNO with M(hfac)2 for M 0/NiII and CoII were prepared in crystalline form according to Scheme 2. [19] CV of these complexes shows irreversible

Scheme 2. Preparation of 2-PyBNO and M(2-PyBNO)(hfac)2.

130

F.A. Villamena et al. / Inorganica Chimica Acta 342 (2003) 125 /130 istry, vol. 1, JAI Press, Greenwich, CT, 1990, pp. 253 /295; (c) L. Eberson, Advances in Physical Organic Chemistry, vol. 31, Academic Press, New York, 1998, pp. 91 /141. [3] F.A. Villamena, M.H. Dickman, D.R. Crist, Inorg. Chem. 37 (1998) 1446. [4] F.A. Villamena, D.R. Crist, J. Chem. Soc., Dalton Trans. (1998) 4055. [5] (a) H.M. Swartz, J.R. Bolton, D.C. Borg, Biological Applications of Electron Spin Resonance, Wiley, New York, 1972; (b) N. Kocherginsky, H.M. Swartz, Nitroxide Spin Labels. Reactions in Biology and Chemistry, CRC Press, Boca Raton, FL, 1995; (c) K. Makino, T. Hagiwara, A. Hagi, M. Nishi, A. Murakami, Biochem. Biophys. Res. Commun. 172 (1990) 1073; (d) B.R. Gibney, J.S. Johansson, F. Rabanal, J.J. Skalicky, A.J. Wand, P.L. Dutton, Biochemistry 36 (1997) 2798. [6] (a) A. Caneschi, D. Gatteschi, R. Sessoli, in: D. Gatteschi, O. Kahn, J.S. Miller, F. Palacio (Eds.), Molecular Magentic Materials, Kluwer Academic Publishers, Dordrecht, 1991, pp. 215 /232; (b) A. Caneschi, D. Gatteschi, P. Rey, Prog. Inorg. Chem. 39 (1991) 331; (c) J.P. Sutter, M. Fettouhi, L. Li, C. Michaut, L. Ouahab, O. Kahn, Angew. Chem., Int. Ed. Engl. 35 (1996) 2113; (d) J.-P. Sutter, M.L. Kahn, S. Golhen, L. Ouahab, O. Kahn, Chem. Eur. J. 4 (1998) 571. [7a] C. Ahlers, M.H. Dickman, Inorg. Chem. 37 (1998) 6337. [7b] P. Bar-On, M. Mohsen, R. Zhang, E. Feigin, M. Chevion, A. Samuni, J. Am. Chem. Soc. 21 (1999) 8070. [8] G.L. McIntire, H.N. Blount, H.J. Stronks, R.V. Shetty, E.G. Janzen, J. Phys. Chem. 84 (1980) 916. [9] B.J. Acken, D.E. Gallis, J.A. Warshaw, D.R. Crist, Can. J. Chem. 70 (1992) 2076. [10] (a) P. Krzyczmonik, H. Scholl, J. Electroanal. Chem. 335 (1992) 233; (b) J.M. Bobbitt, C.L. Flores, Heterocycles 27 (1988) 509; (c) G.I. Shchukin, V.A. Ryabinin, I.A. Gregorev, L.B. Volodarskii, J. Gen. Chem. USSR 56 (1986) 753. [11] S.D. Rychnovsky, R. Vaidyanathan, T. Beauchamp, R. Lin, P.J. Farmer, J. Organomet. Chem. 64 (1999) 6745. [12] S. Morris, G. Sosnovsky, B. Hui, C.O. Huber, N.U.M. Rao, H.M. Swartz, J. Pharm. Sci. 80 (1991) 149. [13] L.B. Volodarsky, V.A. Reznikov, V.I. Ovcharenko, Synthetic Chemistry of Stable Nitroxides, CRC Press, 1994, pp. 3 /8. [14] H.F. Holtzclaw, A.H. Carlson, J.P. Collman, J. Am. Chem. Soc. 78 (1956) 1838. [15] G.S. Patterson, H.R. Holm, Inorg. Chem. 11 (1972) 2285. [16] R.F. Handy, R.L. Lintvedt, Inorg. Chem. 13 (1974) 893. [17] D.T. Sawyer, A. Sobkowiak, J.L. Roberts, Electrochemistry for Chemists, second ed., Wiley, New York, 1995. [18] M.H. Dickman, L.C. Porter, R.J. Doedens, Inorg. Chem. 25 (1986) 2595. [19] F.A. Villamena, M.H. Dickman, D.R. Crist, Inorg. Chem. 37 (1998) 1454. [20] Y.Y. Lim, R.S. Drago, Inorg. Chem. 11 (1972) 1334.

redox systems and no peaks near the E 0/0.69 V peak of PyBNO alone. One can, therefore, conclude that Ep values given in Table 2 are those corresponding to metal nitroxides and not dissociated species. Since oxidation occurs at more positive potentials than the 0.69 V peak of 2-PyBNO, it appears that delocalization of the unpaired electron of the nitroxide to d orbitals of the metal centers, as supported by their X-ray structures and magnetic properties, [19] makes it harder to remove the electron from the complex. These CV results provide additional evidence that 2-PyBNO can be stabilized by complexation. 3.4. Lewis basicity of nitrones vs. nitroxides Lewis basicity generally increases as the oxidation potential becomes less positive, [14] and it is, therefore, of interest to compare values of the present Epa with those of other ligands, some of which are shown in Table 4. Nitrone 2-PyBN gave a higher Epa value (1.38 V) than M3PO (1.17 V), consistent with structural effects previously reported [8]. Nitroxides TEMPO, CPNO, and 2-PyBNO gave the least positive Epa values. In support of a relatively strong Lewis basicity of nitroxides, as suggested by these Epa, Lim and Drago found that TEMPO was comparable to amines in forming complexes with alcohols, boron trifluoride, and Cu(hfac)2 on the basis of electrostatic and covalent susceptibility parameters [20]. However, the presence of an unpaired N /O electron may contribute to a more facile electrochemical oxidation compared with other ligands of Table 4.

Acknowledgements The authors wish to thank Professor Faye Rubinson for helpful discussions.

References
[1] (a) E. Breuer, H.G. Aurich, A. Nielsen, Nitrones, Nitronates, and Nitroxides, Wiley, New York, 1989; (b) K.B.G. Torssell, Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis, VCH Publishers, New York, 1988; (c) K.V. Gothelf, K.A. Jorgensen, Chem. Rev. 98 (1998) 863. [2] (a) E.G. Janzen, Methods Enzymol. 105 (1984) 188; (b) E.G. Janzen, D.L. Haire, Advances in Free Radical Chem-