Metal complexes of meso-tetra-(p-chlorophenyl)porphyrin and meso-tetra-(p-bromophenyl)porphyrin: Tl[(p-Cl)4tpp](OAc) and In[(p-X)4tpp](OAc) [X = Cl, Br, tpp = 5,10,15,20-tetraphenylporphyrinate]

Article abstract of DOI:10.1016/S0277-5387(03)00330-9

The crystal structures of acetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)₄tpp](OAc) (1), acetato-[mesotetra(p-chlorophenyl)porphyrinato]indium(III) In[(p-Cl)₄tpp](OAc) (2) and acetato-[meso-tetra(p-bromophenyl)porphyrinato]indium(III) In[(p-Br)₄tpp](OAc) (3) were determined. The coordination sphere around the Tl³⁺ ion in 1 is described as six-coordinate distorted square-based pyramid in which the apical site is occupied by a chelating bidentate OAc^- group, whereas for the In³⁺ ion in 2 and 3, it is a five-coordinate regular square-based pyramid in which the unidentate OAc^- ligand occupies the axial site. The plane of the four pyrrole nitrogen atoms [i.e. N(1)-N(4)] strongly bonded to Tl³⁺ (or In³⁺) is adopted as a reference plane 4N. The Tl³⁺ is moderately out of the 4N plane; its displacement of 0.69 ? is in the same direction as that of the acetate oxygen for 1. The In³⁺ are located at 0.57 ? from its 4N plane for 2 and 3. The free energy of activation at the coalescence temperature T_c for the intermolecular acetate exchange for 1 in CD₂Cl₂ is found to be ΔG₂₀₀^≠ = 42.54 kJ mol^-1 whereas the intermolecular OAc^- exchange for acetato-[meso-tetra(p-bromophenyl)porphyrinato]thallium(III) Tl[(p-Br)₄tpp](OAc) (4) in CD₂Cl₂ is determined to be ΔG₂₀₀^≠ = 42.46 kJ mol^-1 through ¹H NMR temperature-dependent measurements. Moreover, the two oxygen atoms of the acetato group for 2 and 3 are asymmetrically and chelating bidentately bound to the indium atom in CD₂Cl₂ (or CDCl₃) solvent.

Full text of DOI:10.1016/S0277-5387(03)00330-9

Polyhedron 22 (2003) 1633ꢃ1639
/
www.elsevier.com/locate/poly
Metal complexes of meso-tetra-(p-chlorophenyl)porphyrin and
meso-tetra-(p-bromophenyl)porphyrin: Tl[(p-Cl)4tpp](OAc) and
In[(p-X)4tpp](OAc) [Xꢀ
/
Cl, Br, tppꢀ
/
5,10,15,20-
tetraphenylporphyrinate]
Yu-Yi Lee a, Jyh-Horung Chen a, Hsi-Ying Hsieh b,*
a Department of Chemistry, National Chung-Hsing University, Taichung 40227, Taiwan, ROC
b Chung Hwa College of Medical Technology, Tainan 717, Taiwan, ROC
Received 7 January 2003; accepted 21 February 2003
Abstract
The crystal structures of acetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)4tpp](OAc) (1), acetato-[meso-
tetra(p-chlorophenyl)porphyrinato]indium(III) In[(p-Cl)4tpp](OAc) (2) and acetato-[meso-tetra(p-bromophenyl)porphyrinato]in-
dium(III) In[(p-Br)4tpp](OAc) (3) were determined. The coordination sphere around the Tl3ꢁ ion in 1 is described as six-coordinate
distorted square-based pyramid in which the apical site is occupied by a chelating bidentate OAcꢂ group, whereas for the In3ꢁ ion
in 2 and 3, it is a five-coordinate regular square-based pyramid in which the unidentate OAcꢂ ligand occupies the axial site. The
plane of the four pyrrole nitrogen atoms [i.e. N(1)ꢀ
/
N(4)] strongly bonded to Tl3ꢁ (or In3ꢁ) is adopted as a reference plane 4N. The
˚
Tl3ꢁ is moderately out of the 4N plane; its displacement of 0.69 A is in the same direction as that of the acetate oxygen for 1. The
In3ꢁ are located at 0.57 A from its 4N plane for 2 and 3. The free energy of activation at the coalescence temperature Tc for the
˚
intermolecular acetate exchange for 1 in CD2Cl2 is found to be DG2"00
ꢀ
42.54 kJ molꢂ1 whereas the intermolecular OAcꢂ exchange
/
for acetato-[meso-tetra(p-bromophenyl)porphyrinato]thallium(III) Tl[(p-Br)4tpp](OAc) (4) in CD2Cl2 is determined to be DG2"00
ꢀ
/
42.46 kJ molꢂ1 through 1H NMR temperature-dependent measurements. Moreover, the two oxygen atoms of the acetato group for
2 and 3 are asymmetrically and chelating bidentately bound to the indium atom in CD2Cl2 (or CDCl3) solvent.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Crystal structures; Thallium meso-tetra-(p-chlorophenyl)porphyrin; Indium meso-tetra-(p-chlorophenyl)porphyrin; Indium meso-tetra-
(p-bromophenyl)porphyrin
1. Introduction
Upon replacing tpp2ꢂ with (p-Cl)4tpp2ꢂ and (p-Br)4-
tpp2ꢂ, the complex Tl(tpp)(OAc) became acetato-
[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III)
Tl[(p-Cl)4tpp](OAc) (1) and acetato-[meso-tetra(p-bro-
Our earlier work reported on the molecular structures
(acetato)(meso-tetraphenylporphyrinato)thalliu-
of
mophenyl)porphyrinato]thallium(III)
Tl[(p-Br)4tpp]-
m(III) Tl(tpp)(OAc) [1,2] and (acetato)(meso-tetraphe-
nylporphyrinato)indium(III) In(tpp)(OAc) [3]. The
electron density and the donating ability of the pyrrole
nitrogen, which is the first bonding atom toward the
thallium (or indium) ion in the thallium (or indium)
porphyrin complex, are considered to be lowered in the
case of H2(p-Cl)4tpp [or H2(p-Br)4tpp], as it contains an
electron-withdrawing chlorine (or bromine) atom [4].
(OAc) (4), and complex In(tpp)(OAc) became acetato-
[meso-tetra(p-chlorophenyl)porphyrinato]indium(III)
In[(p-Cl)4tpp](OAc) (2) and acetato-[meso-tetra(p-bro-
mophenyl)porphyrinato]indium(III)
In[(p-Br)4tpp]-
(OAc) (3). The acetate is bidentately coordinated to
the Tl and In atom in Tl(tpp)(OAc) and In(tpp)(OAc),
respectively. However, the introduction of Cl (or Br) in
the para position of the benzene ring of complexes 1ꢃ4
/
might cause a change in the bonding of the acetate to the
Tl atom in 1, 4 and to the In atom in 2, 3 from the
* Corresponding author.
0277-5387/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00330-9

1634
Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ1639
/
chelating bidentate type as observed in Tl(tpp)(OAc)
and In(tpp)(OAc).
was dissolved in CH2Cl2, dried over anhydrous Na2SO4
and filtered. The filtrate was layered with MeOH to
afford purple crystals of 2 (0.116 g, 84%) for single-
In this paper, we reported the X-ray structural
determination of three new porphyrin complexes namely
1, 2 and 3. Prompted by the earlier studies on the acetate
exchange of Tl(tpp)(OAc) observed in CD2Cl2, we
investigated a similar intermolecular exchange for com-
plexes 1 and 4 in CD2Cl2 by 1H and 13C dynamic NMR
methods.
1
crystal X-ray analysis. H NMR (499.85 MHz, CDCl3,
20 8C): d 9.02 (s, Hb, 8.31 [d, 3J(Hꢀ
/
H)ꢀ
7 Hz] for phenyl ortho protons (o-H);
H)ꢀ H)ꢀ8 Hz]
8 Hz] and 7.72 [d, 3J(Hꢀ
for phenyl meta protons (m-H); 0.06 (s, OAc). 13C
NMR (125.70 MHz, CDCl3, 20 8C): d 176.0 (s, OAcꢀ
/
7 Hz] and 8.02
3
[d, J(Hꢀ
/
H)ꢀ
/
7.78 [d, 3J(Hꢀ
/
/
/
/
/
CO); 149.5 (s, Ca); 140.3 (s, C1); 136.0 (s) and 135.2 (s)
for phenyl-C2,6; 134.5 (s, C4); 132.5 (s, Cb); 127.0 (s,
2. Experimental
C
3,5); 120.4 (s, Cm); 18.2 (s, OAcꢀ
(assignment, rel. intensity): 1017 ([In(p-Cl)4tpp(OAc)]ꢁ,
5.21), 865 ([In(p-Cl)4tpp]ꢁ, 100), 753 ([H2(p-
/
Me). MS, m/z
2.1. Preparation of Tl[(p-Cl)4tpp](OAc) (1)
,
Cl)4tpp]ꢁ, 10.22). UVꢃ
/
Vis spectrum, l (nm) [o ꢄ
10ꢂ4
/
A mixture of H2[(p-Cl)4tpp] (0.1 g, 1.33ꢄ
in CH2Cl2 (50 ml) and Tl(OAc)3 (0.15 g, 3.99ꢄ
/
10ꢂ4 mol)
10ꢂ4
(Mꢂ1 cmꢂ1)] in CH2Cl2: 326 (4.4), 406 (8.9), 427
(135.8), 561 (4.6), 600 (1.7).
/
mol) in MeOH (10 ml) was refluxed for 1 h. After
concentrating, the residue was dissolved in CH2Cl2,
dried over anhydrous Na2SO4 and filtered. The filtrate
was layered with MeOH to afford purple crystals of 1
(0.13 g, 87%) for single-crystal X-ray analysis.
2.3. Preparation of In[(p-Br)4tpp](OAc) (3)
Compound 3 in 66% yield was prepared in the same
way as described for 2 using H2[(p-Br)4tpp]. Compound
3 was dissolved in CH2Cl2 and layered with MeOH to
obtain purple crystals for single-crystal X-ray analysis.
1H NMR (599.95 MHz, CDCl3, 20 8C): d 9.03 (s, Hb,
8.26 (d) and 8.24 (d) for phenyl ortho protons (o-H);
1H NMR (599.95 MHz, CD2Cl2, 20 8C): d 9.06 [d,
3
Hb,4J(Tlꢀ
/
H)ꢀ
/
64 Hz], 8.25 [d, J(Hꢀ
/
H)ꢀ8 Hz] and
/
3
8.04 [d, J(Hꢀ
/
H)ꢀ8 Hz] for phenyl ortho protons (o-
/
3
3
H); 7.79 [d, J(Hꢀ
Hz] for phenyl meta protons (m-H); ꢂ
NMR (599.95 MHz, CD2Cl2, ꢂ90 8C): d 9.07 [d, Hb,
64 Hz], 8.19 [d, J(HꢀH)ꢀ8 Hz] and 7.97
H)ꢀ8 Hz] for phenyl ortho protons (o-H);
7.74 [d, 3J(Hꢀ 8 Hz] and 7.62 [d, 3J(Hꢀ
H)ꢀ H)ꢀ8 Hz]
for phenyl meta protons (m-H); ꢂ0.06 [d, OAc, J(Tlꢀ
H)ꢀ
14.4 Hz]. 13C NMR (125.70 MHz, CDCl3, 20 8C):
d 173.7 (s, OAcꢀ
140.2 [d, C1, 4J(Tlꢀ
/
H)ꢀ
/
8 Hz] and 7.71 [d, J(Hꢀ
/
H)ꢀ8
/
/
0.02 (s, OAc). 1H
7.96ꢃ
(d) and 7.86 (d) for phenyl meta protons (m-H); ꢂ
(s, OAc). 13C NMR (150.87 MHz, CDCl3, 20 8C): d
176.3 (s, OAcꢀCO); 149.4 (s, Ca); 140.8 (s, C4); 136.3 (s)
and 135.5 (s) for phenyl-C2,6; 132.5 (s, Cb); 129.9 (s,
3,5); 122.8 (s. C1); 120.4 (s, Cm); 18.1 (s, OAcꢀMe).
MS, m/z (assignment, rel. intensity): 1043 ([In(p-
Br)4tpp]ꢁ, 21.64); 963 ([In(p-Br)4tppꢃBr]ꢁ, 3.32).
UVꢃVis spectrum, l (nm) [o ꢄ
10ꢂ4 (Mꢂ1 cmꢂ1)] in
/7.93 (m) for phenyl ortho and meta protons; 7.85
/
/
0.08
4J(Tlꢀ
/
H)ꢀ
/
/
/
3
3
[d, J(Hꢀ
/
/
/
/
/
/
/
4
/
/
C
/
/
2
/
CO); 149.8 [d, Ca, J(Tlꢀ
C)ꢀ
27 Hz]; 136.0 [d, 5J(Tlꢀ
Hz] and 135.3 [d, J(TlꢀC)ꢀ22 Hz] for phenyl-C2,6
134.6 (s, C4); 132.5 [d, Cb, 3J(Tlꢀ
C)ꢀ119 Hz]; 127.0 (s,
146 Hz]; 18.3 (s, OAcꢀ
Me). 13C NMR (150.87 MHz, CD2Cl2, ꢂ
90 8C): d
242 Hz]; 148.7 [d, Ca,
16 Hz]; 139.1 [d, C1, 4J(Tlꢀ
C)ꢀ27 Hz];
135.5 [d, 5J(Tlꢀ 21 Hz] and 135.2 [d, 5J(Tlꢀ
C)ꢀ C)ꢀ21
Hz] for phenyl-C2,6; 133.3 (s, C4); 132.2 [d, Cb, J(Tlꢀ
C)ꢀ117 Hz]; 126.5 (s) and 126.4 (s) for C3,5; 120.3 [d,
Cm, 3J(Tlꢀ Me, 3J(Tlꢀ
C)ꢀ146 Hz]; 17.7 [d, OAcꢀ C)ꢀ
/
C)ꢀ/15 Hz];
/
/
/
/
C)ꢀ
/
22
/
/
5
/
/
;
CH2Cl2: 325 (60), 407 (113), 419 (139), 523 (9.8), 562
(61), 602 (26).
/
/
3
C
3,5); 120.9 [d, Cm, J(Tlꢀ
/
C)ꢀ
/
/
/
2.4. Preparation of Tl[(p-Br)4tpp](OAc) (4)
2
173.8 [d, OAcꢀ
/
CO, J(Tlꢀ
/
C)ꢀ
/
2J(Tlꢀ
/
C)ꢀ
/
/
/
Compound 4 was prepared in the same way as
1
described for 1 using H2[(p-Br)4tpp]. H NMR (600.13
/
/
/
/
3
/
MHz, CD2Cl2, 20 8C): d 9.05 [d, Hb, 4J(Tlꢀ
/
H)ꢀ
/
63 Hz],
8 Hz]
H)ꢀ
8 Hz] for phenyl meta
0.04 (s, OAc). 1H NMR (600.13 MHz,
90 8C): d 9.07 [d, Hb, 4J(Tlꢀ
H)ꢀ64 Hz];
8.11 [d, 3J(Hꢀ
H)ꢀ8 Hz] for o-H; 7.88 (m) for o-H and
m-H; 7.75 [d, 3J(Hꢀ
H)ꢀ8 Hz] for phenyl meta protons
(m-H); ꢂ H)ꢀ
0.08 [d, OAc, 4J(Tlꢀ 15.1 Hz]. 13C NMR
(150.90 MHz, CD2Cl2, 20 8C): 150.0 [d, Ca, 2J(Tlꢀ
C)ꢀ
16 Hz]; 140.8 [d, C1, 4J(Tlꢀ 27 Hz]; 136.5 [d, 5J(Tlꢀ
C)ꢀ
C)ꢀ C)ꢀ22 Hz] for phenyl-
22 Hz] and 135.9 [d, 5J(Tlꢀ
2,6; 122.9 (s, C4); 132.7 [d, Cb, J(Tlꢀ
/
8.19 [d, 3J(Hꢀ
for phenyl ortho protons (o-H); 7.94 [d, J(Hꢀ
Hz] and 7.88 [d, 3J(Hꢀ
H)ꢀ
protons (m-H); ꢂ
CD2Cl2, ꢂ
/
H)ꢀ
/
8 Hz] and 7.99 [d, 3J(Hꢀ
/
H)ꢀ
/
3
/
/
/
/
/
/
/
8
292 Hz]. MS, m/z (assignment, rel. intensity): 1158
([Tl(p-Cl)4tpp(OAc)]ꢁ, 1.56), 955 ([Tl(p-Cl)4tpp]ꢁ,
/
/
/
36.87), 752 ([H(p-Cl)4tpp]ꢁ, 25.21). UVꢃ
/
Vis spectrum,
10ꢂ4 (Mꢂ1 cmꢂ1)] in CH2Cl2: 336 (23.5),
/
/
/
l (nm) [o ꢄ
/
/
/
434 (205), 568 (19.2), 607 (10.2).
/
/
/
/
/
2.2. Preparation of In[(p-Cl)4tpp](OAc) (2)
/
/
/
/
/
Free base H2[(p-Cl)4tpp] (0.1 g, 1.33ꢄ
In2O3 (0.11 g, 1.45ꢄ
10ꢂ4 mol) were refluxed for 12 h in
50 cm3 of acetic acid. After concentrating, the residue
/
10ꢂ4 mol) and
/
/
/
3
/
C
/
C)ꢀ
/
116 Hz];
3
130.2 (s, C3,5); 121.2 [d, Cm, J(Tlꢀ
/
C)ꢀ
/
146 Hz]. 13C

Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ
/
1639
1635
NMR (150.90 MHz, CD2Cl2, ꢂ
OAcꢀ C)ꢀ
CO, 2J(Tlꢀ 242 Hz]; 148.4 [d, Ca, 2J(Tlꢀ
C)ꢀ16 Hz]; 139.3 [d, C1, J(Tlꢀ
5J(Tlꢀ
phenyl-C2,6; 121.7 (s, C4); 132.1 [d, Cb, J(Tlꢀ
Hz]; 129.2 (s) and 129.1(s) for C3,5; 120.2 [d, Cm, 3J(Tlꢀ
/
90 8C): d 173.8 [d,
2.6. Crystallography
/
/
/
/
4
/
/
C)ꢀ
/
27 Hz]; 135.7 [d,
22 Hz] and 135.5 [d, J(TlꢀC)ꢀ27 Hz] for
C)ꢀ117
Table 1 presents the crystal data as well as other
CHCl3.
Measurements were taken on a Bruker SMART CCD
5
/
C)ꢀ
/
/
/
information for 1×
/
CHCl3, 2×
/
CHCl3 and 3×
/
3
/
/
/
diffractometer using monochromatized Mo Ka radia-
3
˚
0.71073 A). The SADABS and the empirical
C)ꢀ
/
146 Hz]; 17.6 [d, OAcꢀ
/
Me, J(Tlꢀ
/
C)ꢀ/292 Hz].
tion (lꢀ
/
absorption corrections were made for 1×
/
CHCl3 and 2×
/
CHCl3 (or 3×CHCl3), respectively. The structures were
/
2.5. Spectroscopy
solved by direct methods (SHELXTL PLUS) and refined
by the full-matrix least-squares method. All non-hydro-
gen atoms were refined with anisotropic thermal para-
meters, whereas all hydrogen atom positions were
calculated using a riding model and were included in
the structure factor calculation. Tables 2 and 3 list
selected bond distances and angles for these three
complexes.
1H and 13C NMR spectra in CDCl3 or CD2Cl2 (99.6%
from Aldrich) were recorded at 599.95, 600.1 or 499.85
and 150.87, 150.91 or 125.70 MHz, respectively, on
Varian Unity Inova-600 Bruker DMX-600 or Varian
Unity Inova-500 spectrometers locked on deuteriated
1
solvent, and referenced to the solvent peak. H NMR is
7.24 or 5.30 and 13
relative to CDCl3 or CD2Cl2, at dꢀ
NMR to the centre line of CDCl3 or CD2Cl2 at dꢀ
/
C
77.0
/
or 53.6. Next, the temperature of the spectrometer probe
was calibrated by the shift difference of the methanol
resonance in the 1H NMR spectrum. Heteronuclear
multiple quantum coherence was used to correlate
protons and carbon through one-bond coupling and
heteronuclear multiple bond coherence for two- and
3. Results and discussion
3.1. Molecular structures of 1×
CHCl3
/
CHCl3, 2×
/
CHCl3 and 3×
/
three-bond protonꢃ/carbon coupling.
The molecular frameworks for complexes 1ꢃ3 are
/
IR spectra of 2 and H2(p-Cl)4tpp were recorded at
25 8C in KBr discs on a Bruker EQUINOX 55 spectro-
meter.
The positive-ion fast atom bombardment mass spec-
trum (FAB MS) was obtained in a nitrobenzyl alcohol
matrix using a JEOL JMS-SX/SX 102A mass spectro-
depicted in Figs. 1 and 2. Their structures are a six-
coordinate thallium and a five-coordinate indium, hav-
ing four nitrogen atoms of the porphyrins in common,
but they are different with a chelating bidentate OAcꢂ
ligand for 1×
/
CHCl3 and a unidentate OAcꢂ ligand for
2×CHCl3 and 3×
/
/
CHCl3. The metalꢃligand bond dis-
/
meter. UVꢃ
/
Vis spectra were recorded at 25 8C on a
tances, i.e. from the thallium(III) and indium(III) to the
ligand and the angles are summarized in Tables 2 and 3.
HITACHI U-3210 spectrophotometer.
Table 1
Crystal Data for 1×
/
CHCl3, 2×
/
CHCl3 and 3×/CHCl3
Empirical formula a
Formula weight
Space group
Z
C47H28Cl7N4O2Tl (1×
1133.25
¯
P1
/
CHCl3)
C47H28Cl7InN4O2 (2×
1043.70
¯
P1
/
CHCl3)
C47H28Br4Cl3InN4O2 (3×
1221.54
¯
P1
/
CHCl3)
/
/
/
2
2
2
Unit cell dimensions
˚
a (A)
˚
10.6430(8)
14.590(1)
15.550(1)
67.776(1)
77.501(1)
84.254(1)
2181.7(3)
1.725
10.5984(6)
14.6383(8)
15.6115(9)
67.611(1)
77.423(1)
84.266(1)
2185.3(2)
1.586
10.6153(6)
14.7442(7)
15.7201(8)
68.296(1)
77.541(1)
85.221(1)
2232.1(1)
1.817
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
V (A )
˚
Dcalc (g cmꢂ3
Radiation, l (A)
)
˚
Mo, 0.71073
293(2)
4.175
Mo, 0.71073
294(2)
1.014
Mo, 0.71073
295(2)
4.334
Temperature (K)
Absorption coefficient (mmꢂ1
)
b
R
Rw (%)
(%)
3.36
9.93
3.57
9.36
4.28
10.15
0.943
c
Goodness-of-fit
0.866
1.026
a
Including solvate molecules.
b
c
Rꢀ
/
[ajjFojꢂ
/
jFcjj/ajFoj].
Rwꢀ
/
{a[w(Fo2ꢂ
/
Fc2)2]/a[w(Fo2)2]}1/2; wꢀ
/
A/(s2FoꢁBFo2).
/

1636
Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ1639
/
Table 2
is also classified as chelating bidentate. This classifica-
tion is supported by a larger spread of TlꢀO distances
found in the crystal structure of thallium(III) acetate
˚
monohydrate, varying from 2.17(1) to 2.78(2) A [5,6]. It
is further substantiated by dimethyl(2-thioorotato)thal-
˚
Selected bond lengths (A) and angles (8) for 1×
/
CHCl3 and 2×CHCl3
/
/
Compound 1×
Bond lengths
/
CHCl3
Tlꢀ
Tlꢀ
C(45)ꢀ
C(45)ꢀ
C(45)ꢀ
/
O(1)
2.193(4)
2.779(5)
1.172(8)
1.266(8)
1.541(9)
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
/
N(1)
N(2)
N(3)
N(4)
2.195(3)
2.204(3)
2.186(3)
2.219(3)
/O(2)
/
lium(III) monohydrate, TlMe2Tot×
ited TlꢀO distances ranging from 2.668(9) to 2.86(1) A
[7]. This type of bidentate interaction was also pre-
viously observed for Tl(NꢀMeꢀtpp)(OAc)2 with Tl(1)ꢀ
2.223(5) A and Tl(1)ꢀ
Hence all the oxygen atoms [i.e. O(1) and O(2)] are
certainly coordinated to the thallium atom in 1×CHCl3.
/H2O, which exhib-
/
O(1)
O(2)
C(46)
/
˚
/
/
/
/
/
/
/
Bond angles
O(1)ꢀTlꢀO(2)
O(1)ꢀC(45)ꢀO(2)
O(1)ꢀ
O(1)ꢀ
O(1)ꢀ
O(1)ꢀ
O(2)ꢀ
O(2)ꢀ
O(2)ꢀ
O(2)ꢀ
˚
˚
O(4)ꢀ2.746(7) A [8].
O(3)ꢀ
/
/
/
/
/
49.8(2)
124.7(6)
100.9(2)
122.7(2)
114.2(2)
93.9(2)
N(1)ꢀ
N(1)ꢀ
N(1)ꢀ
N(2)ꢀ
N(2)ꢀ
N(3)ꢀ
C(45)ꢀ
C(45)ꢀ
/
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
/
N(2)
N(3)
N(4)
N(3)
N(4)
N(4)
84.2(1)
143.5(1)
84.1(1)
85.0(1)
143.0(1)
84.0(1)
77.2(4)
107.9(4)
/
/
/
/
/
/
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
Tlꢀ
/
N(1)
N(2)
N(3)
N(4)
N(1)
N(2)
N(3)
N(4)
/
/
/
/
/
/
The geometry around Tl in 1 is a distorted square-
based pyramid in which the apical site is occupied by a
chelating bidentate OAcꢂ group, whereas that around
the In3ꢁ in 2 and 3 is described as a regular squared-
based pyramid with N(1), N(2), N(3) and N(4) lying in
the basal plane. Because of the larger size of Tl3ꢁ, Tl lies
/
/
/
/
/
/
/
/
/
/
126.6(2)
81.4(1)
/
O(2)ꢀ
O(1)ꢀ
/
Tl
Tl
/
/
/
/
/
/
85.8(2)
/
/
132.6(2)
˚
0.69 A above the 4N plane toward the acetate oxygen
Compound 2×
Bond lengths
In(1)ꢀO(1)
In(1) O(2)
O(1)ꢀ
O(2)ꢀ
/
CHCl3
˚
for 1×
/
CHCl3, compared to 0.57 A for In(1) in 2×
/
CHCl3
and 3×
/
CHCl3. The OAcꢂ ligand is bidentately coordi-
/
2.088(2)
2.936(2)
1.258(4)
1.242(4)
1.501(5)
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
/
N(1)
N(2)
N(3)
N(4)
2.148(2)
2.139(2)
2.170(2)
2.150(2)
nated to the Tl atom in 1, 4 and Tl(tpp)(OAc) (Table 4).
Moreover, the structure of 2 and 3 is quite different
from that of In(tpp)(OAc) (Table 4). In In(tpp)(OAc),
the OAcꢂ ligand is bidentately coordinated to the In
atom whereas in 2 and 3, it is unidentate. Such a
difference in structure can be explained, that the tetra(p-
chloro)- and tetra(p-bromo)-substitution favors the
unidentate coordination either in 2 or in 3. Similar
observation is made for the trifluoroacetate ligand being
unidentately coordinated to the Tl atom in Tl[(p-
Cl)4tpp](O2CCF3) whereas in Tl(tpp)(O2CCF3) it is
chelating bidentate [9].
/
Á Á Á
/
/
/
C(45)
/
/
C(45)
/
C(45)ꢀ
Bond angles
C(45)ꢀO(1)ꢀ
O(1)ꢀC(45)ꢀ
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
/C(46)
/
/
In(1)
114.9(2)
122.7(3)
115.8(1)
111.28(9)
94.29(9)
98.87(9)
N(1)ꢀ
N(1)ꢀ
N(1)ꢀ
N(2)ꢀ
N(2)ꢀ
N(3)ꢀ
/
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
/
N(2)
N(3)
N(4)
N(3)
N(4)
N(4)
86.85(7)
149.62(8)
85.87(7)
85.84(8)
149.13(9)
85.46(7)
/
/
O(2)
/
/
/
/
N(1)
N(2)
N(3)
N(4)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Table 3
The dihedral angles between the mean plane of 4N
and the planes of the phenyl groups are 43.98 [C(24)],
˚
Selected bond lengths (A) and angles (8) for 3×
/
CHCl3
75.18 [C(30)], 69.58 [C(36)] and 49.48 [C(42)] for 1×
CHCl3 and the corresponding angles are 69.78 [C(24)],
73.68 [C(30)], 47.58 [C(36)] and 49.68 [C(42)] for 2×
CHCl3, and 70.18, 73.28, 48.78, 47.98 for 3×CHCl3. The
radii of the central ‘hole’ [Ct N, the distance from the
Á Á Á
geometrical centre (Ct) of the mean plane of the 4N-
/
Compound 3×
Bond lengths
In(1)ꢀO(1)
In(1) O(2)
Á Á Á
In(1)ꢀN(1)
/
CHCl3
/
/
2.083(3)
2.907(3)
2.151(3)
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
/
N(2)
2.135(3)
2.171(3)
2.147(3)
/
/
/N(3)
/
/
/N(4)
/
/
Bond angles
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
O(1)ꢀIn(1)ꢀ
N(2)ꢀIn(1)ꢀ
/
/
N(1)
115.9(1)
111.1(1)
94.4(1)
N(1)ꢀ
N(1)ꢀ
N(1)ꢀ
N(2)ꢀ
N(3)ꢀ
/
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
In(1)ꢀ
/
N(2)
N(3)
N(4)
N(3)
N(4)
87.0(1)
149.4(1)
85.5(1)
85.7(1)
85.7(1)
˚
atom core to the porphyrinato-core N atoms] are 2.09 A
/
/
N(2)
N(3)
N(4)
/
/
˚
˚
for 1×
/
CHCl3, 2.08 A for 2×
/
CHCl3 and 2.07 A for 3×
/
/
/
/
/
˚
CHCl3 which are larger than 2.01 A as suggested by
Collins and Hoard [10]. The thallium(III) and indiu-
m(III) are bonded in a modestly expanded porphyrinato
/
/
99.4(1)
/
/
/
/
N(4)
148.9(1)
/
/
core (C20N4) in 1×
/
CHCl3 and 2×
/
CHCl3 (or 3×
/
CHCl3),
˚
Bond distances (A) are Tlꢀ
2.779(5), and the mean Tlꢀ
CHCl3; for 2×CHCl3 the values are In(1)ꢀ
2.088(2), and the mean In(1)ꢀN(p)ꢀ2.152(2). Similarly,
bond distances (A) are In(1)ꢀO(1)ꢀ2.083(2) and the
mean In(1)ꢀN(p)ꢀ2.151(3) for 3×CHCl3. Although the
O(2) atom is at a 2.779(5) A distance from the thallium,
which is considerably longer than the TlꢀO(1) distance,
the interaction of the acetate with thallium in 1×CHCl3
/
O(1)ꢀ
/
2.193(4), Tlꢀ
2.201(3) for 1×
O(1)ꢀ
/
O(2)ꢀ
/
individually.
/
N(p)ꢀ
/
/
/
/
/
3.2. 1H and 13C NMR of complexes 1ꢃ
CD2Cl2
/
4 in CDCl3 and
/
/
˚
/
/
/
/
/
When a 0.02 M solution of 1 in CD2Cl2 (Fig. 3) was
cooled, the methyl proton signals of OAcꢂ, being a
single peak at 20 8C (dꢀ
˚
/
/
ꢂ
/
0.02 ppm), first broadened
/
(coalescence temperature Tcꢀ
/
ꢂ
/
73 8C) and then split

Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ
/
1639
1637
Fig. 1. Molecular configuration and atom-labelling scheme for (a) 1×
/
CHCl3 and (b) 2×CHCl3, with ellipsoids drawn at 30% probability. Hydrogen
/
atom and solvent CHCl3 for both compounds are omitted for clarity.
into two peaks with a separation of 14.4 Hz at ꢂ
/
90 8C.
temperature, but would lead to the loss of coupling
between acetate and thallium at higher temperatures.
The chemical shift in the high-temperature limit is the
average for two species (i.e. Tl[(p-Cl)4tpp](OAc) and
OAcꢂ) in Eq. (1) weighted by their concentration [11].
As the exchange of OAcꢂ within 1 is reversible, the
results at 599.95 MHz confirm the separation as a
4
coupling of J(Tlꢀ
/
H). As a result of this observation,
the most likely cause of loss of coupling should be due to
reversible dissociation of acetate
At ꢂ90 8C, the rate of intermolecular exchange of
/
OAcꢂ for 1 in CD2Cl2 is slow and hence at low
Tl[(p-Cl)4tpp](OAc)XTl[(p-Cl)4tpp]ꢁ ꢁOAcꢂ
(1)
temperature, the CO and CH3 of OAcꢂ in 1 are
2
observed at 173.8 ppm [with J(Tlꢀ
/
C)ꢀ242 Hz] and
/
with a small dissociation constant and reasonable rate at
room temperature. Such a scenario would lead to little
change in the chemical shift with temperature and no
detectable free OAcꢂ and Tl[(p-Cl)4tpp]ꢁ at low
17.7 ppm [with 3J(Tlꢀ
/
C)ꢀ292 Hz], respectively. At
/
20 8C, intermolecular exchange of the OAcꢂ group is
rapid, indicated by singlet signals due to carbonyl

1638
Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ1639
/
Fig. 2. Molecular configuration and atom-labelling scheme for 3×
/CHCl3, with ellipsoids drawn at 30% probability. Hydrogen atom and solvent
CHCl3 are omitted for clarity.
carbons at 173.7 ppm and methyl carbons at 18.3 ppm.
cmꢂ1. This Dn value that is significantly greater than
The free energy of activation DG2"00
ꢀ
/
42.54 kJ molꢂ1 is
therefore determined for the intermolecular exchange of
those of the ionic complex denote a unidentate forma-
tion [12]. In addition, X-ray diffraction analysis un-
ambiguously confirms that 2 is a unidentate complex. In
a series of tetraarylporphyrins with Ga, In, Tl, Ge or Sn
as the central metal atom, 13C NMR chemical shifts
were shown to be a useful tool for diagnosing whether
acetato ligands were unidentate or bidentate. Uniden-
OAcꢂ in 1. Similarly, DG2"00
ꢀ
/
42.46 kJ molꢂ1 is
evaluated for the intermolecular exchange of OAcꢂ in 4.
The interaction of the carboxylate with the indium of
2 in the solid is purely unidentate, the second carbox-
˚
ylate oxygen, i.e. O(2), being 2.936(2) A from the
indium atom. This finding further confirms the IR
spectroscopic method’s effectiveness in assigning a
bonding type in metalloporphyrin carboxylates [12].
Comparing the vibrational frequencies of 2 with those
of H2(p-Cl)4tpp allows for the bonds to be assigned at
1619 [nasym(CO2)] and 1207 [nsym(CO2)]. Herein, the
frequency difference (Dn) between the asymmetric
tate acetato ligands were located at 20.59
168.291.7 ppm and the bidentate acetato ligands at
18.090.7 and 175.291.6 ppm [3]. The methyl and
carbonyl chemical shifts of the acetato group for 2 in
CDCl3 at 20 8C are separately located at 18.2 and 176.0
ppm (Table 4) suggesting that the acetate is asymme-
trically chelating bidentate coordinated to the indium
atom in 2 in the solution phase (Eq. (2))
/
0.2 and
/
/
/
(nasym) and symmetric (nsym) Cꢀ
/
O vibrations is 412
Table 4
13C NMR and X-ray data of the acetato group on the M[(p-X)4tpp](OAc) complexes with Mꢀ
/
In, Tl and XꢀCl, Br
/
Solid carboxylate binding, found Solution 13C NMR
(ppm)
Solution carboxylate binding b
˚
Compound
X-ray (A) Dlꢀ
/
l2ꢂ
/
l1
a
Mꢀ/O
Mꢀ
/
O?(M
/
Á Á Á
/
O?) Dl
d(CO)
d(CH3)
Tl(tpp)(OAc)
Tl[(p-Cl)4tpp](OAc) (1)
2.299 2.361
2.193 2.779
0.062 bidentate
0.586 bidentate
0.028 bidentate
0.03
173.1
173.8
173.8
18.5
17.7
17.6
bidentate
bidentate
bidentate
Tl[(p-Br)4tpp](OAc)13 (4) 2.352 2.380
2.38 2.41
In(tpp)(OAc)
In[(p-Cl)4tpp](OAc) (2)
In[(p-Br)4tpp](OAc) (3)
2.215 2.322
2.088 2.936
2.083 2.907
0.107 bidentate
0.848 unidentate
0.824 unidentate
176.1
176.0
176.3
18.1
18.2
18.1
bidentate
bidentate
bidentate
NMR data were recorded in CD2Cl2 at ꢂ
/
90 8C for 1, 4 and in CDCl3 for 2, 3 at 20 8C.
l2 and Dlꢀl2ꢂl1ꢀ0.
The structure was obtained by prediction based on Ref. [3].
a
Let Mꢀ
/
Oꢀ
/
l1, Mꢀ
/
O? (or M
/
Á Á Á
/
O?)ꢀ
/
/
/
/
b

Y.-Y. Lee et al. / Polyhedron 22 (2003) 1633ꢃ
/
1639
1639
acetato group of 1 and 4 in CD2Cl2 reveal that the
OAcꢂ group undergoes intermolecular exchange with a
free energy of activation DG2"00
ꢀ
42.54 kJ molꢂ1 for 1
/
and DG2"00
ꢀ
42.46 kJ molꢂ1 for 4.
/
4. Supplementary material
Crystallographic data in CIF format for 1, 2 and 3
have been deposited with Cambridge Data Centre as
CCDC 200322, 200323 and 200324, respectively. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: ꢁ44-1223-336033; e-mail: deposit@
/
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgements
Financial support from the National Research Coun-
cil of the ROC under Grant NSC 91-2113-M-005-015 is
gratefully acknowledged.
Fig. 3. The 599.95 MHz 1H NMR spectra for the axial acetato protons
of Tl[(p-Cl)4tpp](OAc) (1) in CD2Cl2 at various temperatures.
References
[1] J.C. Chen, H.S. Jang, J.H. Chen, L.P. Hwang, Polyhedron 10
(1991) 2069.
[2] S.C. Suen, W.B. Lee, F.E. Hong, T.T. Jong, J.H. Chen, L.P.
Hwang, Polyhedron 11 (1992) 3025.
[3] S.J. Lin, T.N. Hong, J.Y. Tung, J.H. Chen, Inorg. Chem. 36
(1997) 3886.
[4] M. Inamo, N. Kamiya, Y. Inoda, S. Funahashi, M. Nomura,
Inorg. Chem. 40 (2001) 5636.
[5] R. Faggiani, I.D. Brown, Acta Crystallogr., Sect. B 38 (1982)
2473.
ð2Þ
A
similar phenomenon was found for In(p-
[6] M.O. Senge, K.R. Senge, K.J. Regli, K.M. Smith, J. Chem. Soc.,
Dalton Trans. (1993) 3519.
Br)4tpp(OAc) (3). The OAcꢂ ligand is unidentately
coordinated to the In atom for 3 in the solid phase and
asymmetrically chelating bidentate bound to the indium
in the solution phase (Table 4). Moreover, the OAcꢂ
ligand is bidentately coordinated to the indium atom for
In(tpp)(OAc) both in the solid and the solution phase
(Table 4).
[7] M.S. Garcia-Tasende, B.E. Rivero, A. Castineiras, A. Sanchez,
J.S. Casas, J. Sordo, W. Hihler, J. Strahle, Inorg. Chim. Acta 181
(1991) 43.
[8] J.Y. Tung, J.H. Chen, F.L. Liao, S.L. Wang, L.P. Hwang, Inorg.
Chem. 39 (2000) 2120.
[9] Y.Y. Lee, J.H. Chen, H.Y. Hsieh, F.L. Liao, S.L. Wang, J.Y.
Tung, S. Elango, Inorg. Chem. Commun. 6 (2003) 252.
[10] D.M. Collins, J.L. Hoard, J. Am. Chem. Soc. 92 (1970) 3761.
[11] J.P. Jensen, E.L. Muetterties, in: L.M. Jackman, F.A. Cotton
(Eds.), Dynamic Nuclear Magnetic Resonance Spectroscopy,
In conclusion, this work describes one new thallium
complex 1 and two new indium complexes 2 and 3,
characterized by spectroscopic and crystallographic
methods. Dynamic 13C and H NMR spectra for the
Academic Press, New York, 1975, pp. 299ꢃ
/304.
1
[12] G.B. Deacon, R.J. Phllips, J. Coord. Rev. 33 (1980) 227.