The first family of trigonal prismatic M(bidentate)2(monodentate)2 complexes: Synthesis and characterization of halobis(2-amidothiophenolato)triphenylphosphinerhenium(V)

Article abstract of DOI:10.1016/S0277-5387(02)01026-4

The 1:2 reaction of [Re^VOCl₃(PPh₃)₂] with 2-aminothiophenol (H₂atp) in toluene has afforded red-brown [Re^V(atp)₂(Cl)(PPh₃)]. The corresponding bromo and iodo complexes have been similarly obtained from [Re^VO(OEt)Br₂(PPh₃)₂] and [Re^VO(OEt)I₂(PPh₃)₂], respectively. The X-ray structure of the solvate [Re(atp)₂(Cl)(PPh₃)]. 2CH₂Cl₂ has revealed trigonal prismatic geometry for the ReS₂N₂ClP coordination sphere in which the two triangular faces are defined by the S, S,P and N, N, Cl triads. The twist angle between them is 8.0°. The [Re(atp)₂(X)(PPh₃)](X =Cl, Br, I) complexes are diamagnetic (Re^V, spin-paired d²) and in acetonitrile solution these display a quasireversible Re^VI-Re^V response near 0.7 V. Reaction with H₂atp in air converts [Re^V(atp)₂(X)(PPh₃)] to the tris chelate [Re^VI(atp)₃].

Full text of DOI:10.1016/S0277-5387(02)01026-4

Polyhedron 21 (2002) 1597ꢁ1602
/
www.elsevier.com/locate/poly
The first family of trigonal prismatic M(bidentate)2(monodentate)2
complexes: synthesis and characterization of halobis(2-
amidothiophenolato)triphenylphosphinerhenium(V)
Indranil Chakraborty a, Sibaprasad Bhattacharyya a, Animesh Chakravorty a,b,
*
a Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India
b Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560 064, India
Received 7 December 2001; accepted 20 February 2002
Abstract
The 1:2 reaction of [ReVOCl3(PPh3)2] with 2-aminothiophenol (H2atp) in toluene has afforded red-brown [ReV(atp)2(Cl)(PPh3)].
The corresponding bromo and iodo complexes have been similarly obtained from [ReVO(OEt)Br2(PPh3)2] and [ReVO(OE-
t)I2(PPh3)2], respectively. The X-ray structure of the solvate [Re(atp)2(Cl)(PPh3)]×
for the ReS2N2ClP coordination sphere in which the two triangular faces are defined by the S, S,P and N, N, Cl triads. The twist
angle between them is 8.08. The [Re(atp)2(X)(PPh3)](Xꢀ
Cl, Br, I) complexes are diamagnetic (ReV, spin-paired d2) and in
ReV response near 0.7 V. Reaction with H2atp in air converts
/2CH2Cl2 has revealed trigonal prismatic geometry
/
acetonitrile solution these display a quasireversible ReVI ꢁ
/
[ReV(atp)2(X)(PPh3)] to the tris chelate [ReVI(atp)3]. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Rhenium complexes; Trigonal prismatic geometry; 2-Amidothiophenolato complexes
1. Introduction
position specially in terms of chemical synthesis. This
has prompted us to search for such types and the logical
first target is the bischelate system M(bidentate)2(mo-
nodentate)2. Herein we disclose the synthesis and
characterization of the first family representing the
system.
The trigonal prism is rarely favoured over the
octahedron as the geometry of hexacoordination in
molecular transition metal chemistry. Bonding theories
indicate that metal ions with few d-electrons may
assume the rare geometry in combination with strongly
s-donating nonbulky ligands [1ꢁ
WMe6 [4,5] and ZrMe6
trigonal prismatic molecules have remained primarily
/
3]. Model examples are
2ꢂ
[6ꢁ
/
8]. In practice, however,
2. Experimental
confined to the tris chelate family, M(bidentate)3 where
indeed such species were first discovered [9ꢁ
bidentate ligands are formally dianionic and span the
donor types SS [11ꢁ13], SeSe [11], PP [14], NN [15] and
SN [15ꢁ18].
Tris chelates undoubtedly have the advantages of
facile synthesis and convenient geometrical definition in
terms of a threefold axis. However, the paucity of other
types having trigonal prismatic geometry is an untenable
/
11]. The
2.1. General considerations
/
The starting materials [ReOCl3(PPh3)2], [Re-
O(OEt)Br2(PPh3)2] and [ReO(OEt)I2(PPh3)2] were pre-
pared by reported methods [19,20]. 2-Aminothiophenol
was purchased from Fluka (Switzerland). The purifica-
tion and drying of dichloromethane and acetonitrile for
synthesis as well as electrochemical and spectral work
were done as before [21,22].
/
Toluene was distilled over sodium before use. All
other chemicals and solvents were of reagent grade and
were used as received.
* Corresponding author. Tel.: ꢃ
2805
E-mail address: icac@mahendra.iacs.res.in (A. Chakravorty).
/
91-33-472-4436; fax: ꢃ91-33-473-
/
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 0 2 6 - 4

1598
I. Chakraborty et al. / Polyhedron 21 (2002) 1597ꢁ1602
/
UVꢁ
disk), and 1H NMR spectra (CDCl3) were recorded on a
Shimadzu UVPC 1601 spectrophotometer, a Perkinꢁ
/
Vis spectra (CH2Cl2 solution), IR spectra (KBr
2.4. Synthesis of iodobis(2-
amidothiophenolato)triphenylphosphinerhenium(V),
[Re(atp)2(I)(PPh3)] (2c)
/
Elmer 783 spectrometer, and a Bruker FT 300 MHz
spectrometer, respectively. The numbering scheme used
for 1H NMR assignment is the same as in crystal-
lography. Spin-spin structures are abbreviated as fol-
lows: s, singlet; d, doublet; t, triplet; m, multiplet. Cyclic
voltammetry (in MeCN, 0.1M TEAP) was done at a
platinum working electrode under nitrogen atmosphere
on a PAR model 370-4 electrochemistry system [23].
Microanalyses (C, H, N) were performed using a
This was synthesized in the same manner as (2b) using
[ReO(OEt)I2(PPh3)2] (100 mg, 0.098 mmol) and H2atp
(24.4 mg, 0.196 mmol) Yield: (52 mg, 65%). Anal Calc.
for C30H25IN2S2PRe: C, 43.84; H, 3.06; N, 3.41. Found:
C, 43.78; H, 3.11; N, 3.45%. UVꢁ
Vis (lmax, nm (o, Mꢂ1
/
cmꢂ1)): 463(8090); 347(8760). IR (cmꢂ1, KBr pellet):
3250 (NH). 1H NMR (CDCl3) d: H5, H11 7.93 (d, J 7.7
Hz); H2, H8 7.67 (d, J 8.4 Hz). H4, H10 7.12(m); H3,
Perkinꢁ/Elmer 2400 Series II elemental analyzer.
H9 7.12(m); Nꢀ
/
H 13.08(s); aromatic multiplets, 7.33ꢁ
/
7.52.
2.2. Synthesis of chlorbis(2-
amidothiophenolato)triphenylphosphinerhenium(V),
[Re(atp)2(Cl)(PPh3)] (2a)
2.5. Conversion of [Re(atp)2(Cl)(PPh3)] to
[Re(atp)3]
To a solution of [Re(atp)2(Cl)(PPh3)] (100 mg, 0.137
mmol) in 10 ml of toluene was added 17.12 mg (0.137
mmol) of H2atp. The resulting mixture was heated to
reflux for 60 min affording a deep green solution. The
solvent was then removed under reduced pressure and
the solid thus obtained was dissolved in 10 ml of acetone
and kept for slow evaporation for a few days to get the
pure complex which was dried in vacuo over fused
calcium chloride, Yield: (62.3 mg, 83%). The
[Re(atp)2(Br)(PPh3)] and [Re(atp)2(I)(PPh3)] complexes
could be similarly converted to [Re(atp)3].
To a suspension of ReOCl3(PPh3)2 (100 mg, 0.120
mmol) in 10 ml of toluene was added 30 mg (0.240
mmol) of 2-aminothiophenol, (H2atp). The resulting
mixture was heated to reflux for 15 min affording a
reddish brown solution. The solvent was then removed
under reduced pressure, and the solid thus obtained was
dissolved in 5 ml of dichloromethane, and the solution
was subjected to chromatography on a silica gel column
(20ꢄ
/
1 cm; 60ꢁ120 mesh, BDH). A deep reddish brown
/
band was eluted out with a benzene-acetonitrile (25:1)
mixture. Removal of solvent under reduced pressure
afforded the pure complex which was dried in vacuo
over fused calcium-chloride Yield: (57 mg, 65%). Anal
Calc. for C30H25ClN2S2PRe: C, 49.34; H, 3.45; N, 3.84.
2.6. X-ray crystallography
Single crystal of [Re(atp)2(Cl)(PPh3)].2CH2Cl2 were
grown by slow diffusion of hexane into dichloromethane
solution the crystals rapidly lost the solvent of crystal-
lization and crystallinity in air. A crystal was sealed over
the mother liquor for crystallography. Cell parameters
were determined by a least-squares fit of 30 machine-
Found: C, 49.28; H, 3.49; N, 3.87%. UVꢁVis (lmax, nm
/
(o, Mꢂ1cmꢂ1)): 447(11450); 326(5730). IR(cmꢂ1, KBr
1
Cl). H NMR (CDCl3) d:
pellet): 3250(NH), 320(Reꢀ
/
H5, H11 7.80 (d, J 8.1 Hz); H2, H8 7.56 (d, J 8.4 Hz);
H4, H10 7.08 (t, J 7.2 Hz); H3, H9 6.92 (t, J 7.3 Hz).
Nꢀ
/
H, 12.46(s); aromatic multiplets, 7.28ꢁ7.48.
/
centered reflections (1485
/
2u 5
/
288). Data were col-
lected by the v scan technique in the range 385
/
2u 5
/
2.3. Synthesis of bromobis(2-
amidothiophenolato)triphenylphosphinerhenium(V),
[Re(atp)2(Br)(PPh3)] (2b)
508 for [Re(atp)2(Cl)(PPh3)] on a Siemens R3 m/V four-
circle diffractometer with graphite monochromated Mo
˚
Ka (lꢀ0.71073 A) radiation at 25 8C. Two check
/
reflections after each 198 reflections showed no signifi-
cant intensity reduction. All data were corrected for Lp
effects and absorption [24].
To suspension of [ReO(OEt)Br2(PPh3)2] (100 mg,
0.102 mmol) in 10 ml of toluene was added 25.6 mg
(0.204 mmol) of 2-aminothiophenol, H2atp. The same
procedure as in the previous preparation was then
followed affording the reddish brown complex. Yield:
(53.9 mg, 68%). Anal. Calc. for C30H25BrN2S2PRe: C,
46.51; H, 3.25; N, 3.62. Found: C, 46.46; H, 3.29: N,
The metal atom was located from Patterson maps,
and the rest of the nonhydrogen atoms emerged from
successive Fourier synthesis. The structure were refined
by full-matrix least-squares procedures on F2. All
nonhydrogen atoms were refined anisotropically. Hy-
drogen atoms were included at calculated positions.
Calculations were performed using the SHELXTL V5.03
[25] program package. The two dichloromethane mole-
cules in the lattice are disordered. Significant crystal
data are listed in Table 1.
3.65%. UVꢁ
/
Vis (lmax, nm (o, Mꢂ1cmꢂ1): 453(6740);
335(4284). IR (cmꢂ1, KBr pellet): 3252(NH). H NMR
(CDCl3) d: H5, H11 7.89 (d, J 8.0 Hz); H2, H8 7.65 (d,
J 8.3 Hz); H4, H10 7.15 (t, J 7.5 Hz). H3, H9 7.03 (t, J
1
7.4 Hz); Nꢀ
/
H 12.77(s); aromatic multiplets, 7.28ꢁ7.35.
/

I. Chakraborty et al. / Polyhedron 21 (2002) 1597ꢁ
/1602
1599
Table 1
Crystallographic data for [ReV(atp)2(Cl)(PPh3)]×2 CH2Cl2 (2a)
(2a) could indeed be isolated in satisfactory yield. For
the success of the synthesis it is crucial to control both
the reaction time (15 min) and metal: ligand (1:2) mole
ratio. Use of [ReVO(OEt)Br2(PPh3)2] and [ReVO(OE-
t)I2(PPh3)2] in place of [ReVOCl3(PPh3)2] in the above
synthesis afforded the bromo (2b) and iodo (2c) com-
plexes, respectively.
Empirical formula
Formula weight
Crystal system
Space group
C32H28Cl5N2PReS2
899.10
triclinic
¯
P
/1/
˚
a (A)
9.693 (3)
13.529 (5)
14.944 (4)
115.61 (2)
97.78 (2)
92.27 (3)
1740.2 (10)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
˚
V (A )
Z
Dcalc. (Mg mꢂ3
)
1.716
4.067
m (mmꢂ1
)
u Range (8)
1.70ꢁ25.00
0.0744, 0.1796
1.046
/
R
a, wR2 b[I ꢀ2s(I)]
Goodness-of-fit on F2
Our interest in oxorhenium chemistry [29ꢁ31]
/
a
RꢀjjFojꢂjFcjj/SjFoj.
prompted us to examine the above ReVO reagents
incorporating X(Cl, Br, I) and PPh3 coligands as
starting materials for the reaction with H2atp. It was
hoped that ionised H2atp would displace the oxo atom
forming chelate rings of type (1) but with retention of
some X/PPh3 coordination. This happened in practice.
b
wR2ꢀ[Sw(Fo2ꢂFc2)2/Sw(Fo2)2]1/2
.
The twist angle (f) is defined and calculated accord-
ing to a published procedure [26]. In the case of
[Re(atp)2(Cl)(PPh3)], let cen a and cen b be the centroids
of the faces N1, N2, Cl1 and S1, S2, P1, respectively.
The dihedral angles between planes of cen a, cen b, N1
and cen a, cen b S1; cen a, cen b, N2 and cen a, cen b, S2
and cen a, cenb, Cl1 and cen a, cen b P1 are respectively
5.58, 8.88 and 9.78. The average value, 8.08, is taken as
f. The angular parameters for [Re(atp)3] were either
taken directly from the published work or were com-
puted using the available atomic coordinates [15]. Here
the twist angle is 7.98 is the average of the three dihedral
angles 7.48, 7.88 and 8.58 between planes defined in the
same manner as in the case of [Re(atp)2(Cl)(PPh3)].
Selected characterization data for (2aꢁ2c) are given in
/
the Section 2. The complexes are uniformly diamagnetic
corresponding to the spin paired d2 configuration
2
(idealized a1 ) [1]. In solution the complexes display
?
two characteristic allowed bands in the UVꢁ
Their energy decreases slightly as in the order (2a) (447,
326 nm)ꢀ(2b)(453, 335 nm)ꢀ(2c) (463 nm, 347 nm). In
IR the NꢀH stretch is seen as a sharp feature near 3250
cmꢂ1
/Vis region.
/
/
/
.
The two coordinated atp2ꢂ ligands are equivalent in
1
solution giving rise to two H NMR doublets and two
triplets in the aromatic region, 6.5ꢁ
/
8.0 ppm (J, 7.0ꢁ8.5
/
Hz). The NꢀH proton resonance occurs as a character-
/
3. Results and discussion
istic singlet at 12.468, 12.778 and 13.08 ppm for (2a), (2b)
and (2c), respectively. The signal ‘disappears’ upon
addition of D2O to the solution.
3.1. Synthesis and characterization
The bidentate ligand used in the present work is 2-
aminothiophenol (H2atp) which is prone to chelate
metal ions in diionised form as in (1). The basis of this
choice is the
3.2. Crystal and molecular structure
Only complex (2a) afforded single crystals in the form
of loosely held solvate (2a)×/2CH2Cl2 which was stable
only in presence of the mother liquor. A molecular view
of the complex is shown in Fig. 1 and selected bond
parameters are listed in Table 2. The CH2Cl2 molecules
are highly disordered and occupy cavities in the lattice.
The ReS2N2ClP coordination sphere has distorted
trigonal prismatic geometry as in (2a). The synthetic
procedure used always afforded the same complex and
no evidence of the existence of the possible geometrical
isomers could be found. The areas of the triangular faces
defined by S1, S2, P1 and N1, N2, Cl1 are 4.38 and 3.97
proven ability of this ligand to stabilize the trigonal
prismatic geometry upon tris chelation as in [ReVI(atp)3]
[15,16], [TcVI(atp)3] [27] and [MoVI(atp)3] [28].
The reaction of [ReVOCl3(PPh3)2] with H2atp in
boiling toluene afforded a reddish brown solution
from which [ReV(atp)2(Cl)(PPh3)] of coordination type
2
˚
A , respectively. The prism is thus tapered.

1600
I. Chakraborty et al. / Polyhedron 21 (2002) 1597ꢁ1602
/
Table 3
Angular parameters a of [Re(atp)2(Cl)(PPh3)]×2CH2Cl2 and [Re(atp)3]
b
Parameters
[Re(atp)2(Cl)(PPh3)] [Re(atp)3]
D3h
Oh
f (8)
v1 (8)
v2 (8)
u (8)
8.0
113.7ꢁ
80.2ꢁ98.7(90.5)
123.3ꢁ142.7(134.4) 128.2ꢁ
7.9
124.7(119.3) 119.0ꢁ
84.4ꢁ
0
119.8(119.3) 120
60
90
/
/
/
/
95.1(91.4)
90
54.7
/
/
140.3(134.3) 135.6 180
a
Average values are given in parenthesis.
For definition see text.
b
˚
˚
S (2.30 A) lengths in
the average Reꢀ
/
N (1.97 A) and Reꢀ
/
the former are slightly shorter than those (2.00 and 2.35
˚
A, respectively) in [Re(atp)3] [15]. In absence of the third
Fig. 1. Molecular view and atom-labeling scheme for
[Re(atp)2(Cl)(PPh3)]. All nonhydrogen atoms are represented by 30%
thermal probability ellipsoids.
chelate ring the two atp2ꢂ ligands are pulled closer to
the metal in [Re(atp)2(Cl)(PPh3)]. We are unable to
compare the Reꢀ
/
Cl(2.438(3)) and Reꢀ
/
P (2.450(4))
lengths with those in other trigonal prismatic systems,
Certain angular parameters diagnostic of the geome-
try are: twist angle (f), dihedral angle (v1) between one
coordination plane and another, dihedral angle (v2)
between a coordination plane and a triangular face and
angle (u) at the metal site between two donors in trans
positions. In the present complex the f value is 8.08.
since no such system exist. In pseudooctahedral species
ReVꢀ
lie in the ranges 2.31ꢁ
tively.
/
Cl [29ꢁ
/
31] and ReVꢀ
˚
2.39 and 2.46ꢁ2.52 A, respec-
/
P [20,32,33] lengths usually
/
/
The similarity of the properties of (2b) and (2c) with
those of (2a) strongly suggest that the former species
also have gross trigonal prismatic geometry, although
the extent of distortion could be different in the three
species. We thus have here the first examples of the
trigonal prismatic complexes of type M(bidentate)2(mo-
nodentate)2. Further unusual feature of (2) include the
presence of the bulky PPh3 as a ligand and the presence
of the d2 metal ion (ReV). Structurally characterized
trigonal prismatic metal complexes of good standing
The other angles (Table 2) span the ranges: v1, 113.78ꢁ
/
124.78; v2, 80.28ꢁ98.78 and u, 123.38ꢁ142.78. It is
/
/
instructive to compare these parameters with those of
the structurally characterized tris chelate [Re(atp)3] [15]
as well as with those of idealised D3h and Oh geometries
(Table 3).
Whereas the span of the angular parameters of
[Re(atp)2(Cl)(PPh3)] is generally higher, the averages
invariably lie close to those in [Re(atp)3].
(using f B
/
108 as a criterion) generally contain only d0
11,14,15,18,27,28]. We are excluding
Even though the metal oxidation state in
[Re(atp)2(Cl)(PPh3)] is lower than that in [Re(atp)3]
or d1 metal ions [9ꢁ
/
Table 2
˚
Selected bond distances (A) angles (8) and dihedral angles (8) for [Re(atp)2(Cl)(PPh3)]×2CH2Cl2 (2a)
Bond distances
ReꢀN(1)
ReꢀS(1)
ReꢀCl(1)
1.956(11)
2.306(4)
2.438(3)
ReꢀN(2)
ReꢀS(2)
ReꢀP(1)
1.988(12)
2.289(4)
2.450(4)
Bond angles
N(1)ꢀReꢀS(1)
N(2)ꢀReꢀS(1)
N(1)ꢀReꢀN(2)
N(1)ꢀReꢀCl(1)
N(2)ꢀReꢀCl(1)
S(1)ꢀReꢀCl(1)
S(2)ꢀReꢀCl(1)
Cl(1)ꢀReꢀP(1)
79.0(3)
134.0(4)
86.7(5)
N(1)ꢀReꢀS(2)
N(2)ꢀReꢀS(2)
S(1)ꢀReꢀS(2)
N(1)ꢀReꢀP(1)
N(2)ꢀReꢀP(1)
S(1)ꢀReꢀP(1)
S(2)ꢀReꢀP(1)
142.7(3)
79.1(4)
86.5(2)
82.2(3)
81.4(4)
123.3(3)
140.2(4)
81.4(13)
87.5(14)
137.9(2)
128.5(2)
78.1(12)
Dihedral angles
Re, N(1), S(1)ꢁ
Re, N(2), S(2)ꢁ
Re, N(1), S(1)ꢁ
Re, N(2), S(2)ꢁ
Re, Cl(1), P(1)ꢁ
/
Re, N(2), S(2) 124.7
Re, P(1), Cl(1) 119.4
Cl(1), N(1), N(2) 80.2
Cl(1), N(1), N(2) 93.5
Re, N(1), S(1)ꢁ
/
Re, P(1), Cl(1) 113.7
/
/
Re, N(1), S(1)ꢁ
Re, N(2), S(2)ꢁ
Re, Cl(1), P(1)ꢁP(1), S(1), S(2) 97
/
P(1), S(1), S(2) 86.5
/
/
P(1), S(1), S(2) 86.5
/
Cl(1), N(1), N(2) 98.7
/

I. Chakraborty et al. / Polyhedron 21 (2002) 1597ꢁ
/1602
1601
the cases where the geometry is forced by ligand
structure (clathro-chelates) [34].
charge from: The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: ꢃ44-1223-336033; e-
mail: deposit@ccdc.cam.ac.uk or www: http://
/
www.ccdc.cam.ac.uk).
3.3. Metal redox and reaction with H2atp
In acetonitrile solution the [Re(atp)2(Cl)(PPh3)] spe-
cies display a quasireversible cyclic voltrametric re-
sponse near 0.7 V versus SCE (Table 4). The response
Acknowledgements
is assigned to the ReVIꢁ
/
ReV couple, the reduction
We thank the Department of Science and Technology,
and the Council of Scientific and Industrial Research,
New Delhi, for financial support.
potential of which decreases slightly in the order
(2a)ꢀ(2b)ꢀ(2c).
/
/
Upon treating the type (2) species with one mole of
H2atp in boiling toluene in air for 1 h, the PPh3 and Xꢂ
ligands are replaced by atp2ꢂ affording the tris chelate
[Re(atp)3] in excellent yield. In this reaction the metal
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4. Conclusion
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The synthesis and characterization of the first family
of trigonal prismatic complexes, [ReV(atp)2(X)(PPh3)],
belonging to type M(bidentate)2 (monodentate)2 has
been achieved by reacting ReVO reagents with H2atp.
The species are further unusual in having a bulky ligand
(PPh3) and d2 configuration.
Pentavalent rhenium is redox stabilized in the family
by the PPh3, X ligand pair. The complexes react with
H2atp in air affording the tris chelate [ReVI(atp)3] where
the hexavalent metal is stabilized. Further work on the
design and isolation of different molecular trigonal
prismatic chelate type are in progress.
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5. Supplementary material
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 174267 for compound (2a).
Copies of this information may be obtained free of
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Table 4
Cyclic voltametric data in acetonitrile solution (0.1 M TEAP)
a
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Chemists, Wiley, New York, 1974, p. 167.
E1=2=V(DEp=mV)
Compound
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Inorg. Chem. 30 (1991) 410.
/
/
ReVI=ReV
(2a)
(2b)
(2c)
0.72(80)
0.70(120)
0.68(120)
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a
Conditions: working electrode, platinum; reference electrode,
SCE; scan rate 50 mV sꢂ1. E1/2ꢀ1/2 (EpaꢃEpc), where Epa and Epc
are anodic and cathodic peak potentials, respectively, DEpꢀEpaꢂEpc
.

1602
I. Chakraborty et al. / Polyhedron 21 (2002) 1597ꢁ1602
/
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