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Polyhedron 19 (2000) 655–664

Electrochemical and X-ray studies of nickel(II) Schiff base complexes

derived from salicylaldehyde.
Structural effects of bridge substituents on the stabilisation of
the q3 oxidation state
I.C. Santos a, M. Vilas-Boas a, M.F.M. Piedade c,d, C. Freire a,*, M.T. Duarte b,d, B. de Castro a
a
´
CEQUP/Departamento de Quımica, ˆ
Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre 687, P-4169-007 Porto, Portugal
b
´
Instituto Superior Tecnico, ´
Universidade Tecnica de Lisboa, Lisbon, Portugal
c
´
Departamento de Quımica ´
e Bioquımica, ˆ
Faculdade de Ciencias, Universidade de Lisboa, Lisbon, Portugal
d
´
Centro de Quımica Estrutural, I.S.T, Lisbon, Portugal
Received 10 August 1999; accepted 13 January 2000

Abstract

The oxidative chemistry of three Ni(II) complexes with Schiff base ligands derived from salicylaldehyde and diamines with different steric
demands, N,N9-2-methylpropane-2,3-diyl-bis(salicylideneiminate)nickel(II) (1), N,N9-1,2-cyclohexyl-1,2-dyil-bis(salicylideneiminate)-
nickel(II) (2) and N,N9-2,3-dimethylbutane-2,3-diyl-bis(salicylideneiminate)nickel(II) (3), was studied by cyclic voltammetry and
chronoamperometry in N,N9-dimethylformamide and (CH3)2SO. The electrogenerated species were characterised by EPR spectroscopy. All
three complexes exhibited metal-centred oxidised processes and the oxidised products were low-spin six-coordinate Ni(III) species (dz2
ground state) with two solvent molecules axially coordinate. Addition of pyridine resulted in the replacement of solvent molecules with no
changes in the ground state. The crystal structures of compounds 1 and 3 were determined from single crystal X-ray diffraction data, and the
crystal packing for any of the complexes did not show any systematic parallel orientation of any part of the molecules. X-ray structural data
for the Ni(II) complexes provided a rationale for the E1/2 values obtained in the oxidation processes and for the relative energy of the low-
lying excited duplets of the electrogenerated Ni(III) species. q2000 Elsevier Science Ltd All rights reserved.

Keywords: Crystal structures; Electrochemistry; EPR; Nickel(II)/(III) complexes; Schiff base complexes

1. Introduction different coordinating strength and have found the oxidation

products to be solvent dependent [5–15]. Nickel(II) com-
Nickel(II) complexes with N2O2 Schiff base ligands plexes with salicylaldehyde-based ligands (L) are oxidised
derived from salicylaldehyde have long been used as homo- in dimethylformamide (DMF) and (CH3)2SO by a one-elec-
geneous catalysts [1–3]. More recently, the ease of prepa- tron metal-centred process to six-coordinate Ni(III) species,
ration of metal salen-based modified electrodes by oxidative formulated as [NiIIIL(solv)2]q (where solv stands for a
electropolymerisation of metal complexes in poor coordinat- solvent molecule) [5–9]. However, in CH3CN the com-
ing solvents has prompted their use in heterogeneous electro- plexes are oxidatively polymerised at the electrode surface to
catalysis [4]. Knowledge of the role played by structural/ generate electroactive films [10–15], for which the oxidative
electronic effects to control the redox chemistry of these metal behaviour has been shown to be associated with a ligand-
complexes may prove to be critical in the design of new centred process of the surface redox couple [11–13]. The
catalysts. complexes [Ni(salen)] and [Ni(saltMe)] (see Scheme 1
We have been studying the oxidative chemistry of Ni(II) for an explanation of the abbreviations used) exhibit in strong
complexes with N2O2 Schiff base ligands in solvents with coordinating solvents (DMF and (CH3)2SO) a quasi-revers-
ible diffusion-controlled one-electron transfer process [8],
in which the value of E1/2 of [Ni(salen)] is less positive
* Corresponding author. Tel: q351-22-608 2890; fax: q351-22-608 (approximately 0.07 V in DMF and 0.09 V in (CH3)2SO)
2959; e-mail: acfreire@fc.up.pt than that of [Ni(saltMe)], a behaviour suggested to arise

0277-5387/00/$ - see front matter q2000 Elsevier Science Ltd All rights reserved.
PII S 0 2 7 7 - 5 3 8 7 ( 0 0 ) 0 0 3 0 0 - 4

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656 I.C. Santos et al. / Polyhedron 19 (2000) 655–664

received. Tetraethylammonium perchlorate (TEAP; Fluka,

puriss) was kept in an oven at 608C prior to use. Caution:
perchlorates are hazards and may explode.
The ligands H2saldMe, N,N9-2-methylpropane-2,3-dyil-
bis(salicylideneimine), and H2salhd, N,N9-1,2-cyclohexyl-
1,2-dyil-bis(salicylideneimine), and the respective Ni(II)
complexes were prepared by standard methods [16]; in
H2salhd the cyclohexane in the imine bridge exists as a mix-
ture of the cis and the trans isomers. The synthesis, spectro-
scopic and cyclic voltammetric studies in DMF and
Scheme 1.
(CH3)2SO of the Ni(II) complex with N,N9-2,3-dimethyl-
butane-2,3-diyl-bis(salicylideneiminate), [Ni(saltMe)],
from steric repulsions imposed on axial binding by the axially have been published previously [8]. X-ray quality crystals
oriented methyl groups of the imine bridge [8]. of [Ni(saldMe)] and [Ni(saltMe)] were obtained by slow
In CH3CN the electrogenerated polymers exhibit, in the evaporation of solutions of the corresponding complexes in
oxidative redox switching, quite different properties in terms CH3CN–CH3Cl.
of stabilisation; poly[Ni(saltMe)] reveals high stability/ [Ni(saldMe)], C18H18N2O2Ni. Anal. Calc.: C, 61.2; H,
durability, and conductivity in CH3CN (even for very thick 5.1; N, 7.9. Found: C, 61.6; H, 5.2; N, 7.8%. 1H NMR
polymers) and for a wide potential window [11], a behaviour (CDCl3, 298 K, d): 7.41 (2H, _CH), 7.27–7.01 (6H, aro-
to be contrasted with that of poly[Ni(salen)], a poor con- matic H), 6.59–6.50 (2H, aromatic H), 3.26 (2H, –CH2),
ducting polymer with very low stability [10]. Since these 1.50 (6H, –C(CH3)2. Electronic spectra (800–250 nm), lmax
two nickel complexes differ in four methyl substituents of (´, moly1 dm3 cmy1): in (CH3)2SO, 558 (133), 444
the ethylenimine bridge, we decided to investigate the effect (2460), 410 (5900), 388 (3318), 342 (7146), 321 (7482);
of a smooth increase in the bulkiness of the imine bridge in DMF, 559 (137), 444 (3317), 411 (6545), 386 (3614),
substituents on the solution redox properties of salen-based 344 (7911), 324 (8455).
Ni(II) complexes in (CH3)2SO and DMF, and on the redox [Ni(salhd)], C20H20N2O2Ni. Anal. Calc.: C, 63.3; H, 5.3;
properties of their electrogenerated polymers in CH3CN. N, 7.4. Found: C, 63.3; H, 5.2; N, 7.4%. 1H NMR (DMSO-
The work presented here describes the redox characteris- d6, 298 K, d): 7.71 (2H, _CH), 7.38–7.34 (2H, aromatic
ation of [Ni(saldMe)] (1) and of [Ni(salhd)] (2) in H), 7.20–7.11 (2H, aromatic H), 6.70–6.66 (2H, aromatic
CH3SO and DMF; the results in CH3CN will be published H), 6.53–6.50 (2H, aromatic H), 3.11 (4H, –C6H10), 1.77
elsewhere. The ligand, H2saldMe, has only two methyl (2H, –C6H10), 1.25 (4H, –C6H10). Electronic spectra (700–
groups in the imine bridge, albeit on the same carbon atom, 250 nm), lmax (´, moly1 dm3 cmy1): in (CH3)2SO, 557
and the ligand H2salhd, has the nitrogen atoms bound to two (133), 443 (3227), 410 (6588), 390 (4152), 345 (7410),
consecutive carbons of a cyclohexane (Scheme 1). These 324 (7914); in DMF, 557 (127), 444 (2509), 412 (5717),
ligands provide intermediate situations between those of 392 (3264), 345 (6528), 322 (7443).
H2salen and H2saltMe. Cyclic voltammetry and chronoam- Details on the electrosynthesis of Ni(III) complexes and
perometry were used to characterise electrochemically the the preparation of their pyridine adducts have been described
complexes; chronoamperometric data are also included for elsewhere [5,8].
[Ni(saltMe)] (3). The molecular and crystal structures of
[Ni(saldMe)] and [Ni(saltMe)] have been solved and are 2.2. Physical measurements
reported here. Cyclic voltammetric data for [Ni(saltMe)]
have been published elsewhere [8], but a brief description Elemental analyses (C, H and N) were performed at the
´
Departamento de Quımica, Universidade de Aveiro, Portu-
of the key features are included to provide a complete and
coherent framework for the overall study reported here. gal. 1H NMR spectra were recorded with a Bruker AC 200
spectrometer at 258C, using SiMe4 as internal reference. Elec-
tronic spectra of Ni(II) complexes were recorded with a
Unicam UV2 spectrophotometer at room temperature, in a
2. Experimental standard 1-cm quartz cuvette, using solutions of the ligands
(1=10y5 mol dmy3) or of the metal complexes (1=10y3
2.1. Reagents, solvents, ligands and complexes and 1=10y5 mol dmy3) in DMF and (CH3)2SO. EPR spec-
tra were obtained with a Bruker ESP 300 spectrometer (X-
The solvents for syntheses were of reagent grade and those band) at 120 K; the magnetic field was calibrated by using
for electrochemical studies were of analytical grade; all were Mn2q in MgO and diphenylpicrylhydrazyl was used as inter-
used as received. All reagents (nickel acetate tetrahydrate, nal reference (dpph; gs2.0037). The reported EPR para-
salicylaldehyde, 2-methyl-2,3-propanediamine, 1,2-cyclo- meters were obtained by spectral simulation using the
hexanediamine) were obtained from Aldrich and used as program WinEPR Simfonia (Bruker) and assuming rhombic

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 I.C. Santos et al. / Polyhedron 19 (2000) 655–664 657

spin hamiltonians; line widths were typically in the range electrode cell was used, with a Pt gauze as the working elec-
0.05–0.20 mT. trode, a Pt foil as counter electrode and an Ag/AgCl (1 mol
Electrochemical measurements were performed using an dmy3 NaCl) as reference electrode.
Autolab PGSTAT20 potentiostat/galvanostat. The electro-
chemical cell used in cyclic voltammetry and in double poten-
2.3. Crystallography
tial step chronoamperometry was a closed standard three-
electrode cell connected to a solution reservoir through a
Teflon tube. A Pt disk electrode with an area of 0.0314 cm2 Data were collected at room temperature for
was used as the working electrode, a Pt gauze electrode as [Ni(saldMe)] on an Enraf Nonius TURBOCAD4 diffrac-
the counter electrode and an Ag/AgCl (1 mol dmy3 NaCl) tometer with a copper rotating anode and for [Ni(saltMe)]
as reference electrode. The ferrocene/ferrocinium (Fc/Fc) on an Enraf Nonius MACH3 diffractometer with Mo graphite
redox couple was used as internal standard: under the exper- monochromatised radiation. Data reduction, Lorentz, polar-
imental conditions used, E1/2 for the Fc/Fcq couple was 0.48 isation and empirical absorption corrections were made using
and 0.45 V in DMF and (CH3)2SO, respectively. Prior to the CAD4 software package.
use, the Pt working electrode was polished with an aqueous For both complexes the positions of the nickel atoms were
suspension of 0.05-mm alumina (Buehler) on a Master-Tex obtained from a three-dimensional Patterson synthesis. Three
(Buehler) polishing pad, then rinsed with water and acetone molecules were found in the asymmetric unit of compound
and dried in an oven. All solutions were de-areated and deliv- [Ni(saltMe)], while only one molecule was refined in com-
ered to the cell by a stream of argon. For cyclic voltammetry, plex [Ni(saldMe)]. All the non-hydrogen atoms were
scan rates in the interval 0.005–1.0 V sy1 were used, and the located in subsequent difference Fourier maps, and were
potential limits were 0.0 and 1.3 V. For chronoamperometry refined, on F2, with anisotropic thermal motion parameters.
the potential was stepped from 0.0 V to E1 and back to 0.0 The hydrogen atoms were inserted in calculated positions and
V. After each step the potential was held for 20 s. The applied refined isotropically riding with the parent carbon atom.
potentials E1 were the same for all complexes in DMF and Details for data collection and for structure refinement are
equal to 1.0 V; in (CH3)2SO they were 0.93, 0.90 and 1.0 V presented in Table 1.
for [Ni(saldMe)], [Ni(salhd)] and [Ni(saltMe)], respec- Structure solution and refinement were done with
tively. SHELXS-86 [17] and SHELX-97 [18], and all molecular
Electrolysis were carried out at controlled potential, at a diagrams were drawn with the program ORTEP III [19].
value 0.1 V higher than the anodic peak potential. A three- Atomic scattering factors and anomalous scattering terms

Table 1
Crystal data and structure refinement for [Ni(saldMe)] and [Ni(saltMe)]

Identification code [Ni(saldMe)] [Ni(saltMe)]

Empirical formula C18H18N2NiO2 C20H22N2NiO2
Formula weight 353.09 381.11
Temperature (K) 293(2) 293(2)
Wavelength (A) ˚ 1.54184 0.71069
Crystal system orthorhombic monoclinic
Space group Pcab P21/a
Unit cell dimensions
˚
a (A) 11.521(3) 11.1850(10)
˚
b (A) 15.973(4) 21.640(3)
b (8) 91.040(10)
˚
c (A) 17.414(4) 22.245(2)
Volume (A ˚ 3) 3204.6(14) 5383.4(10)
Z 8 12
Calc. density (Mg my3) 1.464 1.411
Absorption coefficient (mmy1) 1.671 1.096
F(000) 1472 2400
Theta range for data collection (8) 5.08–72.60 1.83–27.00
Index ranges y14FhF0; y19FkF0; y21FlF0 y14FhF14; y27FkF1; y28FlF28
Reflections collected/unique 3182/3182 (Rints0.0000) 24706/11732 (Rints0.0609)
Completeness to 2u (%) 72.60, 96.5 27.00, 97.2
Refinement method full-matrix least-squares on F2 full-matrix least-squares on F2
Data/restraints/parameters 3182/0/205 11732/0/739
Goodness-of-fit on F2 1.105 1.033
Final R indices [I)2s(I)] R1s0.0535; wR2s0.1494 R1s0.0586; wR2s0.1034
R indices (all data) R1s0.0679; wR2s0.1674 R1s0.1278; wR2s0.1344
˚ y3)
Largest difference peak and hole (e A 0.272 and y1.003 0.925 and y0.644

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658 I.C. Santos et al. / Polyhedron 19 (2000) 655–664

were taken from International Tables for Crystallography

[20].

3. Results and discussion

3.1. Spectroscopic characterisation

Ni(II) complexes with the ligands H2saldMe and H2salhd

show electronic spectra in DMF and (CH3)2SO that are very
similar to those of [Ni(saltMe)] and of other Ni(II) Schiff
base complexes derived from salicylaldehyde, both in solu- Fig. 1. Molecular diagram with atomic labelling scheme for [Ni(saldMe)].
tion and in solid. They are characteristic of square planar low- Ellipsoids at 40% probability level [19,38].
spin Ni(II) complexes [21]; typically the spectra exhibit a
low-intensity broad brand at lmaxf550–560 nm (´f125–
135 moly1 dm3 cmy1) assigned to transitions from the four
low-lying orbitals, which is superimposed on a group of high-
intensity charge transfer bands at higher energies (l-
440 nm, ´f2500–500 moly1 dm3 cmy1). The similarity
between the spectra in both solvents and in the solid indicates
that no effective coordination of solvent molecules took place
in any of the solvents.

3.2. Molecular structure

Molecular structure of complexes [Ni(saldMe)] and

[Ni(saltMe)] are depicted in Figs. 1 and 2; relevant bond Fig. 2. Molecular diagram with atomic labelling scheme for molecule B of
lengths and bond angles and the most relevant torsion angles [Ni(saltMe)]. Ellipsoids at 40% probability level [19,38].
are listed in Table 2. The same numbering scheme was used
for the three independent molecules of [Ni(saltMe)]. from planarity. In contrast, the structure of the compound
In both compounds the coordination geometry around the with no substituents in the imine bridge, [Ni(salen)], is
nickel atom is roughly square planar, with the ligands bound almost planar; maximum deviation from planarity of 0.023
through two nitrogen and two oxygen atoms in a cis config- A˚ and with the nickel atom 0.0056 A˚ out of the plane [23].
uration, but with the four N2O2 atoms distorted in a tetrahedral The configuration of the three independent molecules of
fashion. [Ni(saltMe)] is asymmetric umbrella, with NCCN torsion
The maximum deviation from planarity of the coordinated angles of 20(1)8 for molecule A, y43.9(6)8 for molecule B
atoms in [Ni(saltMe)] are 0.074(2), 0.084(2) and and y46.7(5)8 for molecule C; the conformations of the
0.099(2) A ˚ for molecules A, B and C, respectively, while imine bridge are thus cis, gauche and gauche, respectively.
the nickel atom is 0.018(2) A ˚ out of that plane for molecule Deviations of the imine bridge atoms, C3 and C4, from the
˚
A, and 0.016(2) A for molecules B and C. In [Ni(saldMe)], NiN2O2 plane are y0.02(1) and y0.19(1) A ˚ (molecule
the coordination atoms are more distorted towards a tetrahe- ˚
A), y0.619(8) and 0.097(7) A (molecule B) and
dron, with a maximum deviation from planarity of 0.124(1) y0.300(7) and 0.507(7)8 (molecule C). The values of the
A˚ and with the nickel atom 0.013(1) A ˚ out of the plane. The torsion angle for molecules B and C are of the same order of
values of maximum deviation from planarity compare with magnitude as those observed in the homologous ligand
those found for the two independent molecules of derived from naphthaldehyde, [Ni(naptMe)], for which the
[Ni(1R,2R(-)salhd)] [22], which are 0.057 A ˚ for molecule value is 47.5(5)8 [6].
˚
1 and 0.088 A for molecule 2; however, in this molecule the The configuration of the [Ni(saldMe)] molecules is an
nickel atom lies practically within the coordination plane asymmetric umbrella but with the two aldehyde moieties
(y0.0096 and y0.0042 A, ˚ respectively). The values of twisted. The NCCN torsion angle is 39.6(5)8, smaller than
maximum deviation from planarity also compare with those those found in the two crystallographic independent mole-
found for N,N9-1,2-cis-cyclohexane-1,2-diyl-bis(2-hydroxy- cules in the similar complex N,N9-2-methylpropane-2,3-diyl-
acetophenonylidene-iminate)nickel(II), [Ni(a,a9-Me2- bis(3-hydroxysalicylideneiminate)nickel(II), [Ni(3-HO-
salhd)], for which the deviation is 0.076 A ˚ and the nickel saldMe)], [24], which are 44(1) and 45(1)8. The two car-
atom is 0.018 A ˚ out of the plane [7]. It must be pointed that bon atoms, C3 and C4, in [Ni(saldMe)] are below and above
[Ni(salhd)] exists in solution as a mixture of isomers and it the NiO2N2 coordination plane with a quasi-symmetric dis-
is to be expected that they present a comparable deviation placement, y0.365(5) and q0.341(5) A, ˚ respectively.

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 I.C. Santos et al. / Polyhedron 19 (2000) 655–664 659

Table 2
˚ bond angles (8) and torsion angles for [Ni(saldMe)] and [Ni(saltMe)]
Selected bond lengths (A),

[Ni(saldMe)] [Ni(saltMe)]
A molecule B molecule C molecule

Ni–O(1) 1.836(2) 1.844(3) 1.844(3) 1.829(3)

Ni–O(2) 1.845(2) 1.839(3) 1.842(3) 1.835(3)
Ni–N(2) 1.847(2) 1.837(4) 1.846(4) 1.842(4)
Ni–N(1) 1.853(3) 1.843(4) 1.838(4) 1.858(4)
N(1)–C(1) 1.291(4) 1.290(6) 1.290(6) 1.279(6)
N(1)–C(3) 1.502(4) 1.494(6) 1.494(6) 1.499(6)
O(1)–C(11) 1.310(4) 1.297(5) 1.305(6) 1.307(6)
N(2)–C(2) 1.292(4) 1.287(6) 1.278(6) 1.301(6)
N(2)–C(4) 1.462(4) 1.502(7) 1.523(6) 1.498(6)
O(2)–C(21) 1.318(4) 1.297(5) 1.302(5) 1.317(6)
C(1)–C(16) 1.434(4) 1.418(7) 1.427(6) 1.425(7)
C(3)–C(4) 1.517(5) 1.298(9) 1.479(8) 1.544(7)
C(3)–C(6) 1.524(5) 1.875(10) 1.601(8) 1.545(7)
C(3)–C(5) 1.525(5) 1.477(7) 1.521(7) 1.521(7)
C(2)–C(26) 1.422(5) 1.429(6) 1.427(6) 1.433(7)
O(1)–Ni–O(2) 84.41(10) 83.85(14) 84.64(14) 83.79(16)
O(1)–Ni–N(2) 173.07(11) 174.3(2) 173.80(17) 174.75(17)
O(2)–Ni–N(2) 94.77(11) 95.61(16) 95.42(15) 95.17(17)
O(1)–Ni–N(1) 95.34(10) 95.76(16) 94.62(16) 95.60(16)
O(2)–Ni–N(1) 171.63(12) 176.46(17) 175.72(18) 172.88(17)
N(2)–Ni–N(1) 86.47(11) 85.13(18) 85.77(17) 86.07(17)
C(1)–N(1)–C(3) 119.2(3) 120.3(4) 121.4(4) 121.4(4)
C(1)–N(1)–Ni 126.1(2) 125.7(3) 126.9(3) 125.0(4)
C(3)–N(1)–Ni 114.0(2) 113.8(3) 111.5(3) 113.2(3)
C(11)–O(1)–Ni 127.52(19) 126.7(3) 126.1(3) 127.8(3)
C(2)–N(2)–C(4) 120.1(3) 122.3(4) 120.9(4) 122.4(5)
C(2)–N(2)–Ni 126.8(2) 125.1(3) 125.3(3) 125.2(4)
C(4)–N(2)–Ni 112.7(2) 112.6(4) 112.8(3) 112.4(3)
C(21)–O(2)–Ni 127.4(2) 126.4(3) 126.8(3) 126.0(4)
N(1)–C(1)–C(16) 125.0(3) 125.9(5) 124.3(5) 126.5(5)
C(11)–C(16)–C(1) 121.9(3) 121.5(4) 121.5(5) 121.5(5)
O(1)–C(11)–C(16) 123.7(3) 123.8(4) 124.3(4) 123.6(5)
O(1)–C(11)–C(12) 118.8(3) 118.7(4) 118.5(5) 118.4(5)
C(16)–C(11)–C(12) 117.5(3) 117.5(4) 117.1(5) 118.1(5)
N(1)–C(3)–C(4) 103.8(3) 112.1(5) 103.9(4) 103.9(4)
N(1)–C(3)–C(6) 107.0(3) 99.9(5) 107.8(5) 108.0(4)
C(4)–C(3)–C(6) 111.3(3) 86.9(7) 105.7(5) 110.6(4)
N(1)–C(3)–C(5) 113.6(3) 115.6(5) 114.0(5) 112.2(4)
C(4)–C(3)–C(5) 109.5(3) 127.1(6) 113.7(5) 113.7(4)
C(6)–C(3)–C(5) 111.4(3) 105.5(6) 111.0(5) 108.2(5)
N(2)–C(2)–C(26) 125.3(3) 126.0(4) 125.5(4) 125.2(5)
C(21)–C(26)–C(2) 121.5(3) 120.7(4) 121.7(4) 121.7(5)
O(2)–C(21)–C(22) 118.2(3) 119.4(4) 119.7(4) 118.2(6)
O(2)–C(21)–C(26) 123.8(3) 124.3(4) 123.6(4) 123.5(5)
N(2)–C(4)–C(3) 108.7(3) 112.9(6) 106.0(4) 103.1(4)
N(1)–C(3)–C(4)–N(2) 39.6(3) 19.6(13) y43.9(6) y46.7(5)

The maximum deviation from planarity of the coordinated are mainly due to the bulkiness of the substituents in the imine
atoms (and the distance of the nickel atom to the equatorial bridge. The presence of these bulky substituents imposes
plane) in similar molecules which have ethylene-based severe steric requirements due to interactions between the
bridges without substituents or aromatic bridges are 0.033 Å hydrogen atoms, and consequently the three molecules
˚ in [Ni(a,a9-Me2salen)] [7], 0.023 A
(0.0073 A) ˚ (0.0056 [Ni(saldMe)], [Ni(saltMe)] and [Ni(salhd)] are quite
˚ ˚
A) in [Ni(salen)] [23], 0.013 A in [Ni(saloph)] [25], distorted.
˚ (0.0078 A)
0.039 A ˚ in [Ni(3,5-Cl2salophen)] [7] and 0.01 Another key result that emerged from the molecular struc-
˚
A in [Ni(napen)] [26]. We can conclude, when comparing tures is that one methyl group in [Ni(saldMe)] is oriented
the above values with those of [Ni(saldMe)], [Ni(1R,2R- perpendicular to the equatorial plane, and that two methyl
(-)salhd)] and [Ni(saltMe)], that the observed distortions groups in [Ni(saltMe)] are oriented perpendicular to the

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660 I.C. Santos et al. / Polyhedron 19 (2000) 655–664

equatorial plane and in opposite directions. No crystal struc- irreversible nature of charge transfer, it should be noted that
ture is known for [Ni(salhd)] with the cyclohexane in the the peak potential pattern for H2saltMe is quite different from
cis form, but recalling that of [Ni(a,a9-Me2salhd)] it is to that of the other ligands.
be expected the ring to be also axially oriented.
Regarding the Ni–O and Ni–N bonding distances (Table 3.4.2. Nickel complexes
2), they are comparable to those observed in Schiff base Cyclic voltammetric data are summarised in Table 3. The
complexes with identical coordination spheres [6,7,23– results for [Ni(saltMe)] have been published elsewhere [8],
29] and are within the average values found in a Cambridge and this complex shows in both solvents a quasi-reversible
Structural Database search [28,29] for compounds having oxidation of Ni(II) to Ni(III). The cyclic voltammograms
two carbon atoms in the imine bridge. The relative values of of [Ni(saldMe)] and [Ni(salhd)] are solvent dependent; in
Ni–O and Ni–N bond lengths do not follow any pattern and DMF in the potential range used they exhibit one anodic peak
no trend could be established between their values and any and the corresponding cathodic peak. The values of E1/2 (vs.
of the parameters used to characterise molecular distortion. Ag/AgCl) are very similar and the anodic–cathodic peak
potential separations, for the lowest scan rates used, are com-
3.3. Crystal packing parable to that of Fcq/Fc couple, but somewhat higher for
fast sweep rates. The ratio ipc:ipa was found to decrease with
The packing of both [Ni(saldMe)] and [Ni(saltMe)] do increasing scan rates.
not show any Ni∆Ni intermolecular distance below 3.5 A. ˚ The behaviour of [Ni(saldMe)] and [Ni(salhd)] in
In the packing of [Ni(saldMe)] the shorter Ni∆Ni interac- (CH3)2SO is more intricate, since the voltammograms are
˚ and for [Ni(saltMe)] the existence of three
tion is 4.463 A, dependent on scan rate. At low scan rates (0.005–0.02 V
independent molecules with such different orientations in the sy1), two anodic waves, Epa(I) and Epa(II), but only one
asymmetric unit prevents shorter interactions in the crystal cathodic wave, which is related to the first anodic process
packing. The shorter ones, 5.561 and 6.471A, ˚ are between (Epc(I)), could be detected (Fig. 3 and Table 3). As the scan
the nickel atom of molecule A and the nickel atoms of mol- rate increases, a positive shift in Epa(I) and Epa(II) (larger
ecules B and C. Actually, the close intermolecular interac- for the latter process) and an increase in peak current (smaller
tions between molecule A and the surrounding molecules in for the latter process) are observed; furthermore, for scan
the unit cell explain the different conformation found for this rates faster than 0.05 V sy1 only the first anodic wave and
molecule. the corresponding cathodic wave could be observed, as
shown in Fig. 3. The ratio ipc:ipa (Table 3) for the first process
3.4. Cyclic voltammetry is somewhat larger than 1 for low scan rates, but smaller than
1 for the highest scan rates.
3.4.1. Ligands For [Ni(saldMe)] and [Ni(salhd)] in the two solvents,
The three ligands, H2saldMe, H2salhd and H2saltMe, are the dependence of ip with n1/2 was found to be linear at low
irreversibly oxidised in both solvents; the respective anodic scan rates, but to deviate from linearity with increasing sweep
peak potentials (scan rate 0.01 V sy1) are approximately rate. By coupling these results with the observations that,
1.22, 1.26 and 0.88 V in DMF, and 1.17, 1.15 and 0.84 V in with increasing scan rate, the ratios ipc:ipa become smaller
(CH3)2SO. With increasing scan rates all ligands show a than 1 and the anodic–cathodic peak potential separation
positive peak potential shift, as well as an increase in current (DE) becomes larger than the values for Fcq/Fc, it becomes
intensity. Although no comparison between the potential clear that the rate of the electron transfer, relative to that of
peak values of the three ligands can be made due to the the mass transport, is insufficient to maintain the nernstian
Table 3
Cyclic voltammetric data for Ni(II) complexes in DMF and (CH3)2SO (0.1 mol dmy3 TEAP) a

Complex n (V sy1) In DMF In (CH3)2SO

Epa Epc DE E1/2 ipc:ipa EpaI EpaII EpcI DE E1/2 ipc:ipa b

[Ni(salhd)] 0.01 0.87 0.78 0.08 0.83 1.02 0.77 0.91 0.69 0.08 0.73 1.05
c d
1 0.92 0.73 0.19 0.82 0.68 0.87 0.39 0.48 0.65
[Ni(saldMe)] 0.01 0.85 0.78 0.07 0.82 1.02 0.76 0.88 0.70 0.06 0.73 1.05
c d
1 0.89 0.74 0.15 0.82 0.75 0.81 0.63 0.18 0.80
[Ni(saltMe)] 0.01 0.94 0.84 0.10 0.89 1.00 0.86 – 0.78 0.08 0.82 0.93
1 0.94 0.85 0.09 0.90 0.97 0.89 – 0.75 0.14 0.82 0.78
a
All potentials are referred to Ag/AgCl (1 mol dmy3 NaCl).
b
Refers to process denoted as (I).
c
The anodic wave is not detected at high scan rates.
d
Electrochemical process with a high degree of irreversibility.

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 I.C. Santos et al. / Polyhedron 19 (2000) 655–664 661

the solution stability of the electrogenerated Ni(III) species.

The X-ray structure of [Ni(saldMe)] shows one methyl
group oriented towards one axial position which thus will
interact directly with one axially bound solvent molecule in
the oxidised species, weakening the bond to the metal with
the consequent destabilisation of Ni(III) complexes. This
explanation also holds for [Ni(saltMe)], for which two
methyl groups of the imine bridge are directed towards two
opposite axial positions thus weakening axial coordination
of the two solvent molecules in the Ni(III) complexes. There-
fore [Ni(saltMe)] exhibits, as expected, the more positive
E1/2 values for the series of complexes studied. Although no
crystal structure for the cis isomer of [Ni(salhd)] is known,
the preceding discussion suggests that in this isomer the
cyclohexane ring must hinder axial coordination and must
influence markedly its electrochemical responses.
A caveat to the above discussion is that structural data were
obtained in the solid state. In solution, where solid states
effects are absent, it is not possible to rule out the existence
of other conformations of [Ni(saldMe)] and [Ni(salhd)],
and thus the two anodic processes observed at low scan rates
in (CH3)2SO may be due to the oxidation of complexes in
different conformations, one of which does not allow stabi-
Fig. 3. Cyclic voltammograms of [Ni(salhd)] in 0.1 mol dmy3 TEAP– lisation of Ni(III) species.
(CH3)2SO between 0.00 and 1.30 V at different scan rates: (i) 0.005, (ii)
0.010, (iii) 0.020, (iv) 0.050, (v) 0.100, (vi) 0.500, (vii) 1.00 V sy1.
3.5. Chronoamperometry
equilibrium at the electrode surface. The one-electron charge
transfer process is thus reversible and diffusion controlled at In both solvents the current–time responses in chronoam-
low scan rates, whereas at high scan rates a transition to a perometric experiments for [Ni(saldMe)], [Ni(salhd)] and
quasi-reversible mixed (kinetic and diffusion) controlled [Ni(saltMe)], depicted as i versus ty1/2 (Cottrell represen-
process must take place [30]. tation [30]), are straight lines that exhibit small deviations
The oxidation of several N2O2 salicylaldehyde-derived from linearity for long periods, particularly in the reduction
Schiff base Ni(II) complexes has been shown to occur with step (typically longer than 6 s for the oxidation and 2 s for
a concomitant axial coordination of solvent molecules, and the reverse step). These deviations from linearity suggest a
this step proved to be decisive in the overall charge transfer change from a diffusion-controlled process to a mixed con-
process, as it controls the final oxidised products and the trolled process [30], as has been inferred from cyclic voltam-
E1/2 values [5–15]. A similar solvent dependence is also metry in (CH3)2SO. By using the linear region of the Cottrell
operative in the oxidation process of [Ni(salhd)] and equation, the diffusion coefficients for oxidation (DCAoxi)
[Ni(saldMe)], as can be gathered by noting that their E1/2 and the reverse step (DCAred) were calculated and are sum-
values are less positive in (CH3)2SO, the strong coordinating marised in Table 4. The values for DCAoxi are of the same
magnitude as those obtained for the oxidation of [Ni(salen)]
solvent used.
and [Co(salen)] using the Randles–Sevcik equation [31].
The E1/2 values for [Ni(salhd)] and [Ni(saldMe)] in
each solvent are similar, albeit slightly more positive than Table 4
that of [Ni(salen)] [E1/2 (DMF)s0.81 V and E1/2 Values of DCA obtained using the Cottrell equation
((CH3)2SO)s0.70 V; scan rate 0.01 V sy1] and less posi-
tive than that of [Ni(saltMe)]. To account for this behaviour, Complex (CH3)2SO DMF
it must be pointed out that introduction of substituents in the Step 106 DCA Step 106 DCA
imine bridge not only affects the electronic properties of the (V) (cm2 sy1) (V) (cm2 sy1)
complex, but also may impose steric constraints on axial co-
[Ni(saldMe)] 0.0™0.93 4.00 0.0™1.0 9.20
ordination. Electron-donating substituents (methyl groups 0.93™0.0 3.66 1.0™0.0 8.91
and the cyclohexyl) are expected to decrease the values of
[Ni(salhd)] 0.0™0.90 3.68 0.0™1.0 8.91
E1/2, and as such their E1/2 values would be expected to be 0.90™0.0 3.10 1.0™0.0 8.58
less positive than those of [Ni(salen)]. However, the values
[Ni(saltMe)] 0.0™1.0 2.98 0.0™1.0 8.35
obtained were more positive, an indication that steric con- 1.0™0.0 2.65 1.0™0.0 7.35
straints play a more important role than electronic effects in

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662 I.C. Santos et al. / Polyhedron 19 (2000) 655–664

[Ni(saltMe)] and [Ni(salen)] [8], with a solution colour

change from reddish to dark brown. Frozen-solution EPR
spectra of electrolytically generated nickel complexes are
similar in both solvents, and show the rhombic symmetry and
the large g tensor anisotropy typically associated with metal-
centred oxidised species (Fig. 4A). The spectra exhibit no
hyperfine splittings and are similar to those of oxidised solu-
tions of [Ni(saltMe)], [Ni(salen)] [8] and other electro-
generated Ni(III) Schiff base complexes derived from
salicylaldehyde [5–7]. The oxidised complexes can thus be
formulated as six-coordinate, with two solvent molecules
bound axially, [Ni (L) (solv)2]q, and with the metal centre
in a low-spin 2A1 (dz2) ground state. In the absence of EPR
Fig. 4. Frozen-solution X-band EPR spectra at y1408C of (A) an electro- crystal data for the Ni(III) complexes studied, the observed
chemically oxidised solution of [Ni(saldMe)] in DMF, (B) the correspond- similarity between their g features and those of analogous
ing pyridine adduct, and its simulation (C).
Ni(III) compounds [5–9] can be extended to support the
Analysis of DCA shows that: (1) the values in DMF are following orientation scheme for the tensor axes of the nickel
higher than those obtained in (CH3)2SO, and (2) the values complexes: g1sgx, g2sgy, g3sgz, where g1 an g3 refer to
decrease in both solvents in the order [Ni(saldMe)]) the lowest and highest magnetic field g values, respectively.
[Ni(salhd)])[Ni(saltMe)]. Solvent dependence can eas- EPR data for Ni(III) species in DMF and (CH3)2SO are
ily be accounted for by differences in solvent viscosity summarised in Table 5; for comparison the values for
[30,31]: the complexes have smaller DCA values in the sol- [Ni(salen)(X)2]q and [Ni(saltMe)(X)2]q are also
vent with higher viscosity, (CH3)2SO. No straightforward included.
explanation can be invoked for the differences in DCA for the In order to obtain more information on the effect of the
complexes; we note, however, that the smallest value is imine bridge substituents on the electronic properties of six-
obtained for the complex with the longest axial bonds coordinate Ni(III) species, the EPR characterisation was
([Ni(saltMe)(solv)2]q (see EPR section, below), and that extended to compounds with axially bound pyridine mole-
the average size of the Ni(III) complexes may be the key cules. Upon addition of pyridine to freshly prepared solutions
factor in controlling diffusion. of electrogenerated Ni(III) complexes in DMF at tempera-
tures just above the softening point of the frozen glass, new
3.6. Electrolysis and EPR characterisation of the oxidised Ni(III) species are formed, as can be inferred from their
solutions frozen-solution EPR spectra (Fig. 4B). These are of rhombic
type, although with less rhombicity than the parent com-
Electrochemical oxidation of [Ni(saldMe)] and plexes, have smaller values of gav (2.140–2.144) and exhibit
[Ni(salhd)] in DMF and (CH3)2SO proceeds as that of hyperfine couplings in all g regions. The existence of one
Table 5
EPR parameters for [Ni(L)(X)2]q complexes

Complex Experimental values Coefficients a Energy of excited state (cmy1)

b
gx gy gz gav Dxy C1 C2 C3 D(2B1) D(2A2) DQ c

[Ni(salen)(dmf)2]q d 2.266 2.222 2.021 2.170 0.044 0.0343 0.0424 0.1075 11465 9275 3658
[Ni(salen)(Me2SO)2]q d 2.256 2.216 2.020 2.164 0.040 0.0334 0.0399 0.1045 11774 9856 3763
[Ni(salen)(py)2]q d 2.201 2.172 2.021 2.131 0.029 0.0251 0.0298 0.1096 15667 13196 3588
[Ni(salhd)(dmf)2]q 2.267 2.220 2.027 2.171 0.047 0.0330 0.0405 0.1202 11930 9707 3273
[Ni(salhd)(Me2SO)2]q 2.264 2.223 2.026 2.171 0.041 0.0336 0.0402 0.1181 11700 9780 3330
[Ni(salhd)(py)2]q 2.208 2.182 2.030 2.140 0.026 0.0257 0.0299 0.1236 15310 13150 3181
[Ni(saldMe)(dmf)2]q 2.268 2.220 2.027 2.172 0.048 0.0330 0.0407 0.1202 11930 9667 3271
[Ni(saldMe)(Me2SO)2]q 2.263 2.223 2.026 2.171 0.040 0.0336 0.0400 0.1180 11700 9821 3332
[Ni(saldMe)(py)2]q 2.213 2.190 2.030 2.144 0.023 0.0271 0.0309 0.1230 14270 12740 3196
[Ni(saltMe)(dmf)2]q d 2.265 2.224 2.020 2.170 0.041 0.0348 0.0414 0.1053 11300 9499 3734
[Ni(saltMe)(Me2SO)2]q d 2.254 2.226 2.020 2.167 0.028 0.0351 0.0396 0.1047 11204 9931 3756
[Ni(saltMe)(py)2]q d 2.214 2.186 2.022 2.141 0.028 0.0278 0.0324 0.1060 14146 12137 3710
a
Obtained from McGarvey equations; see text.
b
The value of gav was calculated as (gxqgyqgz)/3.
c
Difference between the average energy of the quartet states and the ground state.
d
From [8].

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 I.C. Santos et al. / Polyhedron 19 (2000) 655–664 663

Table 6
14
N superhyperfine coupling constants and spin densities for [NiL(py)2]q complexes

Complex Experimental superhyperfine coupling a Anisotropic super- Spin densities on 14N l2

hyperfine tensor
Ax Ay Az AH b Aiso c Axx,yy Azz C22s C22p Total d (%)

[Ni(salen)(py)2]q e 1.65 1.76 2.14 1.71 1.85 y0.15 0.28 0.033 0.084 23.4 2.5
[Ni(salhd)(py)2]q 1.70 1.65 2.13 1.68 1.83 y0.15 0.29 0.033 0.088 24.1 2.7
[Ni(saldMe)(py)2]q 1.85 1.75 2.15 1.80 1.92 y0.12 0.22 0.034 0.067 20.2 1.9
[Ni(saltMe)(py)2]q e 1.82 1.63 2.14 1.72 1.86 y0.14 0.27 0.033 0.080 22.7 2.4
a
The A values are expressed in mT.
b
AH was calculated as (AxqAy)/2.
c
Aiso could not be obtained for the adducts; instead it was calculated from (AxqAyqAz)/3.
d
Spin density delocalized onto the two axial nitrogen atoms.
e
From [8].

well-resolved quintuplet (As2.15–2.13 mT) in the region in the energy of the doublets, as a result of the strong inter-
of higher magnetic field and of two non-resolved quintuplets action of the pyridine lone pair with the dz2 orbital. This
in the other g regions, implies that solvent molecules have increase lowers the value of the McGarvey coefficients, C2
been substituted by two pyridines (14N; Is1) and that the and C1, and using the g factor equations neglecting second-
resulting Ni(III) complexes have unequivocally a low-spin order terms, gxs2.0023q6C2 and gys2.0023q6C1
2
A1 (dz2) ground state. The similarity between the g pattern [5,8,9], a decrease in gx and gy is predicted, as was actually
of these species with those of the parent complex supports
observed.
the same orientation scheme for the g tensor of the pyridine
Analysis of data in Table 5 reveals also that for the same
adducts.
axial coordinate molecule (XsDMF, (CH3)2SO and py),
No EPR signals were detected in fluid solutions of pyri-
the energy of the excited doublets decreases in the order
dine–DMF or in frozen solution of pyridine adducts in
[Ni(salen)(X)2]q ) [Ni(salhd)(X)2]q G [Ni(saldMe)-
(CH3)2SO, as has also been observed for the homologous
complexes with H2salen and H2saltMe ligands, a conse- (X)2]q ) [Ni(saltMe)(X)2]q. This ordering reflects the
quence of the very fast decomposition rate of the pyridine strength of the axial ligation/axial bond length and thus we
adducts in fluid solutions [5,8,9,32]. EPR parameters for can deduce that axial bond lengths in the Ni(III) complexes
[Ni(L)py2]q are summarised in Tables 5 and 6; values for with saltMe are the weakest (longest), and that those of salen
similar complexes with salen and saltMe are also included. complexes are the strongest (shortest), with the other com-
plexes exhibiting intermediate and similar bond lengths.
3.7. Electronic structure of the Ni(III) species These observations correlate with the sequence of E1/2 values,
and reflects mainly, as mentioned above, steric interactions
of the imine bridge substituents with the axially bound mol-
Analysis of the EPR parameters using the model developed
ecules in Ni(III) complexes.
by McGarvey for d7 systems with an 2A1 (dz2) ground state
[33], in conjunction with the approximation suggested by
Labause and Raynor [34,35], can provide information on the
3.7.1. Nitrogen hyperfine tensor and spin density on
electronic structure of Ni(III) species. A full description of
this analysis is described elsewhere [5,8,9] and its applica- nitrogen atoms of axial bound pyridines
tion allows an estimate of the energy of excited doublet states The 2s and 2p spin densities, the ratio p:s (l2sC22p/C22s)
D(2B1) and D(2A2) and the average energy of the quartet and the total spin density delocalised onto the axially bounded
states DQ, provided the values of complex spin orbit coupling pyridine have been calculated by procedures described else-
constants (j) are known. We have used the j values of [Ni(salt- where [5,8,9,37] and are reported in Table 6. The values of
Me)((CH3)2SO)2]q and [Ni(salen)((CH3)2SO)2]q, C22s are practically insensitive to changes in the equatorial
which were found to be 55% of the free ion [8,36]. In Table ligand, whereas those of C22p show larger variations. Thus
5 are included the values for D(2B1), D(2A2) and DQ for changes in total spin density and in l2 reflect primarily
[Ni(L)(DMF)2]q, [Ni(L)((CH3)2SO)2]q and [Ni(L)- changes in values of C22p. The two new complexes exhibit
(py)2]q. values for the latter quantities that are in the range observed
Analysis of data in Table 6 failed to reveal any correlation for pyridine adducts of Ni(III) complexes with ligands
between the energy of the excited quartets and axial ligation. derived from salicylaldehyde and aliphatic diamines, but no
The energy of the doublet states does not change significantly correlation with the bulkiness of the aliphatic imine bridge
when the solvent is varied from DMF to (CH3)2SO, but the could be extracted from the data, probably due to the limited
axial coordination of pyridine induces a significant increase number of complexes studied.

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664 I.C. Santos et al. / Polyhedron 19 (2000) 655–664

4. Concluding remarks [4] C.E. Dahm, D.G. Peters, J. Electroanal. Chem. Interfacial Electro-
chem. 406 (1996) 119.
[5] B. Castro, C. Freire, Inorg. Chem. 29 (1990) 5113.
The oxidation of [Ni(saldMe)] and [Ni(salhd)] in DMF
[6] M.A.A.F. de C.T. Carrondo, B. Castro, A.M. Coelho, D. Domingues,
and (CH3)2SO (strong donor solvents) was shown to pro- C. Freire, J. Morais, Inorg. Chim. Acta 205 (1993) 157.
ceed through oxidation of the metal centre and with concom- [7] F. Azevedo, M.A.A.F. de C.T. Carrondo, B. Castro, M. Convery, D.
itant axial coordination of solvent molecules, as has been Domingues, C. Freire, M.T. Duarte, K. Nielsen, I.C. Santos, Inorg.
observed for [Ni(salen)] and [Ni(saltMe)], giving Ni(III) Chim. Acta 219 (1994) 43.
complexes formulated as [Ni(L)(solv)2]q, where L is a [8] C. Freire, B. Castro, J. Chem. Soc., Dalton Trans. (1998) 1491.
[9] C. Freire, B. Castro, Polyhedron 17 (1998) 4227.
Schiff base and solv a solvent molecule.
[10] M. Vilas-Boas, C. Freire, B. Castro, A.R. Hillman, P.A. Christensen,
X-ray structure of the complexes revealed that in Inorg. Chem. 36 (1997) 4929.
[Ni(saltMe)] two methyl groups of the imine bridge are [11] M. Vilas-Boas, C. Freire, B. Castro, A.R. Hillman, J. Phys. Chem. B
perpendicular to the equatorial plane and directed towards 102 (1998) 8533.
the two axial coordination positions, whereas in [12] K.A. Goldsby, J. Coord. Chem. 19 (1988) 83.
[Ni(saldMe)] only one methyl group is directed towards [13] K.A. Goldsby, L.A. Hoferkamp, Chem. Mater. 1 (1989) 348.
[14] P. Audebert, P. Capdevielle, M. Maumy, New J. Chem. 15 (1991)
one axial position. It is to be expected also that in the cis
235.
isomer of [Ni(salhd)] the cyclohexane group is directed [15] P. Audebert, P. Capdevielle, M. Maumy, New J. Chem. 16 (1992)
towards one of the axial positions. Thus the required axial 697.
coordination of solvent molecules in these electrogenerated [16] R.H. Holm, G.W. Everett, A. Chakravorty, Prog. Inorg. Chem. 7
Ni(III) species is hindered sterically when compared with (1966) 183.
[Ni(salen)] and the main result is that the sequence observed [17] G.M. Sheldrick, in: G.M. Sheldrick, C. Kurger, R. Goddard (Eds.),
Crystallographic Computing 3, Oxford University Press, Oxford,
for the E1/2 values, [Ni(salen)] - [Ni(salhd)] F [Ni-
1985, p. 175.
(saldMe)] - [Ni(saltMe)], parallels the hindrance on [18] G.M. Sheldrick, A Computer Program for Refinement of Crystal
axial coordination. Thus, bulky substituents in the imine ¨
Structures (SHELXL-97), University of Gottingen.
bridge tend to render less accessible the q3 oxidation state [19] M.N. Burnett, C.K. Johnson, ORTEP III: Oak Ridge Thermal Ellip-
in Ni(II) complexes with the N2O2 Schiff base ligands. soid Plot Program for Crystal Structure Illustrations, Oak Ridge
National Laboratory Report ORNL-6895, 1996.
[20] International Tables for X-Ray Crystallography, vol. IV, Kynoch
Press, Birmingham, 1974.
Supplementary data
[21] G. Maki, J. Chem. Phys. 28 (1958) 651.
´
[22] A. Wojtczak, E. Szlyk, M. Jaskolski, E. Larson, Acta Chem. Scand.
Crystallographic data (excluding structure factors) for the 51 (1997) 274.
structures in this paper have been deposited with the Cam- [23] A.G. Manfredotti, C. Guastini, Acta Crystallogr., Sect. C 39 (1983)
bridge Crystallographic Data Centre as supplementary 863.
publications nos. CCDC 133149 {[Ni(saldMe)]} and [24] U. Casellato, P. Guerriero, S. Tamburini, P.A. Vigato, C. Benelli,
CCDC 133150 {[Ni(saltMe)]}. Copies of the data can be Inorg. Chim. Acta 207 (1993) 39.
obtained, free of charge, on application to CCDC, 12 Union [25] A. Radha, M. Seshasayee, K. Ramalingam, G. Aravamudan, Acta
Crystallogr., Sect. C 41 (1985) 1169.
Road, Cambridge CB2 1EZ, UK, (fax: q44-1223-336033 [26] F. Akhtar, Acta Crystallogr., Sect. B 37 (1981) 84.
or e-mail: deposit@ccdc.cam.ac.uk). [27] M. Calligaris, G. Nardin, L. Randaccio, Coord. Chem. Rev. 7 (1972)
385.
[28] F.H. Allen, O. Kennard, R. Taylor, Acc. Chem. Res. 16 (1983) 146.
Acknowledgements [29] F.H. Allen, J.E. Davies, J.J. Galloy, O. Johnson, O. Kennard, C.F.
Macrae, G.F. Mitchell, G.F. Mitchell, J.M. Smith, D.G. Watson, J.
¸ ˜ para
This work was partially supported by the ‘Fundacao Chem. Inf. Comput. Sci. 31 (1987) 187.
[30] A.J. Bard, L.R. Faulkner, Electrochemical Methods, Wiley, New
ˆ
a Ciencia e Tecnologia’ (F.C.T.) through project PBIC/
York, 1980.
QUI/2137/95. M.V.-B. thanks the FCT/Praxis XXI for a [31] A. Kapturkiewicz, B. Behr, Inorg. Chim. Acta 69 (1983) 247.
fellowship. [32] B. Castro, C. Freire, E. Pereira, J. Chem. Soc., Dalton Trans. (1994)
571.
[33] B.R. McGarvey, Can. J. Chem. 53 (1975) 2498.
References [34] G. Labause, J.B. Raynor, J. Chem. Soc., Dalton Trans. (1980) 2388.
[35] G. Labause, J.B. Raynor, J. Chem. Soc., Dalton Trans. (1981) 590.
[1] C. Gosden, K.P. Healy, D. Pletcher, J. Chem. Soc., Dalton Trans. [36] A.H. Maki, N. Edelstein, A. Davison, R.H. Holm, J. Am. Chem. Soc.
(1978) 972. 86 (1964) 4580.
[2] K.P. Healy, D. Pletcher, J. Organomet. Chem. 186 (1980) 401. [37] B.A. Goodman, J.B. Raynor, Adv. Inorg. Chem. Radiochem. 13
[3] C. Gosden, J.B. Kerr, D. Pletcher, R. Rosas, J. Electroanal. Chem. (1970) 135.
Interfacial Electrochem. 117 (1981) 101. [38] P. McArdle, J. Appl. Crystallogr. 28 (1995) 65.

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