Synthesis, structure and properties of a five-coordinate oxophosphorus(V) meso-triphenylcorrole

Article abstract of DOI:10.1002/ejic.201200651

Treatment of six-coordinate (5,10,15-triphenylcorrole) dihydroxyphosphorus(V) [P(TPC)(OH)₂] with trifluoroacetic acid (TFA) in CH₂Cl₂ for 30 min at room temperature followed by recrystallization gave stable five-coordinate (5,10,15-triphenylcorrole) oxophosphorus(V) [P(TPC)O] in quantitative yield. The formation of [P(TPC)O] from [P(TPC)(OH)₂] in the presence of TFA was also monitored by NMR, absorption and fluorescence spectroscopic titration studies. The structure of the isolated [P(TPC)O] was confirmed by X-ray crystallography. In [P(TPC)O], the corrole ring is distorted, and the P^V ion is displaced by 0.456 A from the N₄ plane towards the axial oxygen atom. This is unlike six-coordinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V) [P(TPC)(OCH₃)₂], in which the P^V ion lies in the porphyrin plane. NMR, absorption and fluorescence spectroscopy and electrochemical studies indicate that [P(TPC)O] exhibits interesting and distinct properties, which differ from the six-coordinate [P(TPC)(OCH ₃)₂]. Attempts to reduce the P^V complex [P(TPC)O] to its corresponding P^III complex by treating it with LiAlH₄ resulted in the formation of six-coordinate (5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)H₂].

Full text of DOI:10.1002/ejic.201200651

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DOI: 10.1002/ejic.201200651
Synthesis, Structure and Properties of a Five-Coordinate Oxophosphorus(V)
meso-Triphenylcorrole
Avijit Ghosh,[a] Way-Zen Lee,[b][‡] and Mangalampalli Ravikanth*[a]
Keywords: Fluorescence / Phosphorus / Coordination modes / Corroles
Treatment of six-coordinate (5,10,15-triphenylcorrole)di-
hydroxyphosphorus(V) [P(TPC)(OH)2] with trifluoroacetic
plane towards the axial oxygen atom. This is unlike six-coor-
dinate (5,10,15-triphenylcorrole)dimethoxyphosphorus(V)
acid (TFA) in CH2Cl2 for 30 min at room temperature fol- [P(TPC)(OCH3)2], in which the PV ion lies in the porphyrin
lowed by recrystallization gave stable five-coordinate
(5,10,15-triphenylcorrole)oxophosphorus(V) [P(TPC)O] in
quantitative yield. The formation of [P(TPC)O] from [P(TPC)-
(OH)2] in the presence of TFA was also monitored by NMR,
absorption and fluorescence spectroscopic titration studies.
The structure of the isolated [P(TPC)O] was confirmed by X-
ray crystallography. In [P(TPC)O], the corrole ring is dis-
torted, and the PV ion is displaced by 0.456 Å from the N4
plane. NMR, absorption and fluorescence spectroscopy and
electrochemical studies indicate that [P(TPC)O] exhibits
interesting and distinct properties, which differ from the six-
coordinate [P(TPC)(OCH3)2]. Attempts to reduce the PV com-
plex [P(TPC)O] to its corresponding PIII complex by treating
it with LiAlH4 resulted in the formation of six-coordinate
(5,10,15-triphenylcorrole)dihydridophosphorus(V) [P(TPC)-
H2].
group-element-containing corrole complexes is their strong
fluorescence behaviour with record high quantum yields as
noted for GaIII and AlIII corroles.[6] Recently, insertions of
phosphorus into new porphyrinoids such as triazacor-
roles,[7] N-fused porphyrins,[8] N-fused telluraporphyrins,[9]
an expanded isophlorin[10] or a triply fused [24]pentaphyrin
have been carried out, and their structural and electronic
properties were studied.[11] Even though the phosphorus ion
is smaller than the usual metal ions and is potentially a
good fit for the small cavity of corroles, there are only three
reports on phosphorus corrole complexes.[12] Paolesse et
al.[12a] reported the first five-coordinate PV corrole com-
Introduction
Corroles are tetrapyrrolic macrocycles, which are closely
related to porphyrins, but because corroles have one direct
pyrrole–pyrrole bond, they have one carbon atom less in
their outer periphery and contain an extra NH proton in
their inner core compared to porphyrins.[1] Thus, corroles
have a –3 charge in their deprotonated form and often lead
to the stabilization of metal ions in high oxidation states[2]
unlike porphyrins, which have a charge of –2 in their depro-
tonated form and stabilize metals in low oxidation states.
Based on these features, one expects that corroles can com-
plex with a large number of metal ions, however, the coordi-
nation chemistry of corroles is largely restricted to transi-
tion metals,[3] and there are only a few examples in the lit-
erature on metallocorroles containing main group ele-
ments.[4] Recently, Gross et al.[5] reviewed the coordination
chemistry of corroles containing main group elements and
discussed their synthesis, spectroscopy, electrochemistry
and crystallography as well as their chemical reactivity and
stability features. The most prominent features of the main-
plex of 8,12-diethyl-2,3,7,13,17,18-hexamethylcorrole
2
(Scheme 1), which contains an axial –OH group as con-
firmed by X-ray analysis. Kadish, Vogel et al.[12b] reported
the synthesis and electrochemical studies of a five-coordi-
nate P=O complex of 2,3,7,8,12,13,17,18-octaethylcorrole
(H3OEC) 3 (Scheme 1) but the crystal structure was not
reported. Gross et al.[12c] reported the synthesis of a six-
coordinate PV complex of 5,10,15-tris(pentafluorophenyl)-
corrole (4, Scheme 1). Except the above-mentioned reports,
to the best of our knowledge, there are no other reports on
PV corroles until our recent report[13] on the synthesis of a
series of six-coordinate PV complexes of meso-triarylcor-
roles such as (5,10,15-triphenylcorrole)dihydroxyphosphor-
us(V) [P(TPC)(OH)2] (5, Scheme 1). The crystal structure
analysis of PV complexes of meso-triarylcorroles supported
six coordination of the PV ion with two axial ligands. How-
ever, our NMR spectroscopic studies indicated the existence
of some amount of the corresponding five-coordinate PV
corrole due to partial dissociation of the six-coordinate PV
[a] Department of Chemistry, Indian Institute of Technology Bom-
bay,
Powai, Mumbai 400076, India
E-mail: ravikanth@chem.iitb.ac.in
Homepage:
mr.html
http://www.chem.iitb.ac.in/people/Faculty/prof/
[b] Department of Chemistry, National
Taiwan Normal University,
88 Sec. 4 Ting-Chow Road, Taipei 11677, Taiwan
E-mail: wzlee@ntnu.edu.tw
[‡] Single-crystal X-ray structure analysis
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200651.
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A. Ghosh, W.-Z. Lee, M. Ravikanth
FULL PAPER
corrole complex upon standing for a long time in non- ture for 30 min followed by recrystallization (Scheme 2).
coordinating solvents. In coordinating solvents, such as The spectral and electrochemical properties of 1 are inter-
CH3OH, CH3CN, dimethyl sulfoxide (DMSO) and tetra- esting and quite distinct from those of six-coordinate PV
hydrofuran (THF), the PV meso-triarylcorrole complexes corrole complex 6. Our attempts to prepare a PIII meso-
exist only as six-coordinate complexes with two solvent mo- triarylcorrole complex by reducing 1 with LiAlH4 resulted
lecules as axial ligands. For example, the six-coordinate in the formation of only the six-coordinate PV corrole com-
complex (5,10,15-triphenylcorrole)dimethoxyphosphorus- plex [P(TPC)H2] (7) with two hydrides as axial ligands
(V) [P(TPC)(OCH3)2] (6, Scheme 1) was obtained as a pure (Scheme 3).
stable compound by treating 5 with methanol followed by
recrystallization. Attempts to isolate a pure five-coordinate
PV meso-triarylcorrole complex from the mixture of corre-
sponding five- and six-coordinate PV corroles were unsuc-
cessful. The six-coordinate PV complexes of meso-triaryl-
corroles, such as 6, are strongly fluorescent with high quan-
tum yields compared to those of weakly fluorescent PV
complexes of meso-tetraarylporphyrins.[14] Furthermore,
the six-coordinate PV meso-triarylcorroles exhibited very
interesting absorption and electrochemical properties com-
pared to those of six-coordinate PV meso-tetraphenylpor-
phyrins. As a five-coordinate PV complex of meso-triaryl-
corrole had not been isolated to date, its properties re-
mained elusive. Herein, we report the synthesis, structure,
spectral and electrochemical properties of a stable five-co-
ordinate neutral PV=O complex of 5,10,15-triphenylcorrole
1 (Scheme 1). Compound 1 was prepared by treating
Scheme 2. Synthesis of 1.
[P(TPC)(OH)2] 5a, which contains a small amount of the
corresponding dissociated five-coordinate PV complex 5b,
with trifluoroacetic acid (TFA) in CH2Cl2 at room tempera-
Scheme 3. Synthesis of 7.
Results and Discussion
The six-coordinate PV corrole complex 5a was prepared
by treating 5,10,15-triphenylcorrole (H3TPC)[15] with POCl3
in pyridine at reflux temperature for 30 min followed by col-
umn chromatographic purification as previously re-
ported.[13] The six-coordinate compound 5a, which contains
hydroxy groups as axial ligands, is generally stable in the
solid state, but in solution it shows partial dissociation to
the corresponding five-coordinate PV corrole complex 5b
leading to mixture of six- and five-coordinate complexes
(Scheme 2). We assume that the five-coordinate complex
formed here contains one axial –OH group. However, we
cannot separate the five- and six-coordinate complexes by
any separation technique. Hence, we prepared stable six-
coordinate PV corrole complexes such as 6 and charac-
terized them by various techniques including X-ray crystal-
lography.[13] In this work, the aim is to isolate a pure five-
coordinate PV meso-triarylcorrole complex and study its
electronic and structural properties. We attempted various
Scheme 1. PV corrole complexes 1–6.
methods to convert the mixture of five- and six-coordinate
2
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A Five-Coordinate Oxophosphorus(V) meso-Triphenylcorrole
complexes (5a and 5b) to the five-coordinate PV meso-triar- phorus centre, and detailed 31P NMR studies on phos-
ylcorrole 1 in pure form. During the course of our investi- phorus derivatives of porphyrins, phthalocyanines and re-
gations, we realized that the five-coordinate corrole 1 can lated macrocycles[16] indicate that six-coordinate phos-
be isolated by treating the mixture of six- and five-coordi- phorus macrocyclic compounds generally show signals in
nate 5a and 5b with TFA at room temperature. The five- the range –180 to –200 ppm, whereas five-coordinate com-
coordinate PV=O complex of meso-triphenylcorrole 1 was pounds show signals in the range –90 to –110 ppm. As ex-
synthesized by treating 5 with excess TFA in CH2Cl2 at pected, the six-coordinate complex 6 showed a signal at
room temperature for 30 min (Scheme 2). The reaction mix- –178 ppm, but 1 showed a signal at –98.5 ppm in 31P NMR
ture changed from pink-violet to red as the reaction pro- spectroscopy (part b of Figure 1 and Table 1), which sup-
gressed. UV/Vis spectroscopy showed the disappearance of ports a five-coordination environment around the phos-
one of the Q-bands at 598 nm corresponding to a six-coor- phorus ion in 1.
dinate complex[13] and an increase in the intensity of the
Furthermore, we followed the conversion of six-coordi-
other two Q-bands at ca. 557 and ca. 522 nm indicating nate 5 to pure five-coordinate 1 by H and 31P NMR, ab-
the formation of the five-coordinate PV meso-triarylcorrole sorption and fluorescence spectroscopic titration studies.
complex 1. The Soret band also experienced a slight blue- The 1H and 31P NMR spectroscopic titration of six-coordi-
shift on the formation of 1. The solvent was removed with nate 5a containing a small amount of dissociated five-coor-
a rotary evaporator and the resultant solid was recrys- dinate 5b was carried out with an increasing amount of
tallized from dry CH2Cl2/n-hexane to afford pure 1 as a TFA in CDCl3 (see S5 and S6, Supporting Information). In
1
1
pink-violet solid in quantitative yield. The composition of the H NMR spectra, upon increasing the quantity of TFA
1 was confirmed by HRMS (see S3 in the Supporting Infor- added to 5 in CDCl3, the more intense sets of four doublet
mation) and characterized by various spectroscopic tech- of doublets at 8.80, 8.97, 9.05 and 9.26 ppm, which corre-
1
niques and X-ray crystallography. A comparison of the H spond to the eight β-pyrrole protons of the six-coordinate
and 31P NMR spectra of pure 6 and 1 is shown in Figure 1. species 5a, gradually disappear. At the same time, the other
It is clear from Figure 1 (a) that 6 exhibits four doublet of four less intense signals corresponding to the eight β-pyr-
doublets at 8.78, 8.95. 9.03 and 9.38 ppm for eight β-pyrrole role protons of the five-coordinate corrole 5b were grad-
4
1
protons due to JP,H coupling in H NMR spectroscopy. ually replaced by four unresolved broad sets of signals at
Upon formation of the five-coordinate PV=O complex 1, 8.94, 9.22, 9.25 and 9.47 ppm (see S5, Supporting Infor-
the sets of four β-pyrrole proton signals broadened and mation) due to the formation of the desired five-coordinate
underwent a slight downfield shift to appear at 8.94, 9.22, 1. This is also clearly evident in the 31P NMR spectra,
9.25 and 9.47 ppm (Table 1). The chemical shift of the which showed complete disappearance of a signal at ca.
phosphorus nucleus in 31P NMR spectroscopy also gives –191.4 ppm corresponding to the six-coordinate 5a with the
information about the coordination number of the phos- appearance of a signal at ca. –98.5 ppm due to the forma-
Figure 1. Comparison of (a) 1H NMR spectra of 1 recorded in CDCl3 and 6 recorded in CD3OD and (b) 31P NMR spectra of 1 recorded
in CDCl3 and 6 recorded in CD3OD at room temperature.
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1
Table 1. Selected H, 31P NMR, absorption, fluorescence, redox and crystallographic structural data for 1 and 6.
Six-coordinate 6
Five-coordinate 1
NMR[a]
1H NMR (β-pyrrole) [ppm]
31P{1H} NMR [ppm]
9.38, 9.03, 8.95, 8.78
–178.0
407 (5.41), 414 (5.36), 505 (sh), 521 (3.96),
9.47, 9.25, 9.22, 8.94
–98.5
405 (5.40), 447 (3.74), 482 (sh), 522 (4.08),
Absorption bands λmax [nm], ( logε)[b]
547 (sh), 559 (4.13), 594 (4.60)
600, 656 (sh)
0.44
557 (4.28)
568, 610 (sh)
0.27
Emission bands λmax [nm][c]
Quantum yield (Φ)
Life time (τ) [ns]
3.01
1.61
0.64, 0.90
Redox potentials [mV][c]
Crystal structure parameters
Crystal system and space group
Corrole ring geometry
0.65, 1.11, 1.28, –1.48
orthorhombic, P21
almost planar
0.005
0.033
1.668, 1.663
1.83
monoclinic, P21/n
distorted
0.456
0.478
1.500
P [d]
Δ4N
Δ23
P [e]
P–O[f]
P–N[g] (average)
1.80
[a] In CD3OD for 6 and in CDCl3 1. [b] In CH3OH for 6 and CH2Cl2 for 1. [c] In CH3OH for 6 and in CH2Cl2 (in presence of trace
amount of TFA) for 1. [d] Displacement [Å] of phosphorus from the mean plane of the four pyrrole nitrogen atoms. [e] Displacement
[Å] of phosphorus from the 23-atom mean plane of the corrole core. [f] Unit: Å. [g] Average value, unit: Å.
tion of the five-coordinate 1 (See S6, Supporting Infor- sponding to six-coordinate[13] 5 and the appearance of a
mation). Furthermore, in the 1H NMR spectroscopic ti- new band at 568 nm due to the formation of five-coordinate
tration of 5, we also observed the complete disappearance 1 (Figure 3).
of the axial OH signal at –4.64 ppm due to formation of 1.
The absorption spectral titration studies also confirmed the
conversion of six-coordinate 5 to five-coordinate 1 in the
presence of TFA. Figure 2 shows the systematic changes in
the absorption spectrum of 5 on addition of increasing
amounts of TFA in CH2Cl2. Addition of TFA to 5 resulted
in the gradual disappearance of the absorption band at
598 nm with a simultaneous increase in the absorption
bands at 557 and 522 nm supporting the formation of five-
coordinate 1. Fluorescence spectral titration studies were
carried out by adding TFA to 5 in CH2Cl2 and resulted in
the disappearance of a fluorescence band at 607 nm corre-
Figure 3. Fluorescence titration of 5 with the addition of increasing
amounts of trifluoroacetic acid (TFA) in CH2Cl2 at room tempera-
ture.
The absorption, electrochemical and fluorescence prop-
erties of isolated five-coordinate 1 were studied and com-
pared with those of six-coordinate 6. The comparison of Q-
and Soret band absorption spectra of 1 and 6 is shown in
Figure 4 (a), and the data are presented in Table 1. As re-
ported previously, six-coordinate 6 shows one strong Q-
band at 594 nm and two or three other weak Q-bands in
addition to one broad strong Soret band at 407 nm with a
shoulder. However, five-coordinate 1 shows two moderately
intense Q-bands at 552 and 557 nm and one sharp strong
Soret band at 405 nm, which was slightly blueshifted com-
pared to that of 6. Interestingly, the strong Q-band at
594 nm for 6 is completely absent in the spectrum of 1.
Figure 2. UV-titration of 5 with the addition of increasing amounts
of trifluoroacetic acid (TFA) in CH2Cl2 at room temperature. An
expansion of the Q-band region 450–645 nm is shown as inset.
4
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A Five-Coordinate Oxophosphorus(V) meso-Triphenylcorrole
PV meso-triarylcorroles indicated that these are as brightly
fluorescent as AlIII and GaIII corroles and the quantum
yields (Φ) and the singlet state lifetimes (τ) are in the range
of 0.33–0.68 and 1.9–3.7 ns, respectively.[13] Five-coordinate
1 also showed a strong emission band at 568 nm, which is
blueshifted compared to that of 6 (Figure 4, b). The quan-
tum yield (Φ) of 1 is 0.27, which is slightly lower than that
of 6. The fluorescence decay of 1 was fitted to a single ex-
ponential curve (see S8, Supporting Information) and the
singlet state lifetime (τ) is 1.61 ns. Thus, 1 is strongly fluo-
rescent, and the fluorescence is diminished compared to
that of 6.
We attempted to prepare a PIII meso-triphenylcorrole
complex by reducing 1 with LiAlH4 in dry ether at reflux
temperature for 20 min.[12b] As the reaction progressed, the
reaction mixture changed from pink-red to green and fi-
nally to greenish violet. The crude compound was purified
by alumina column chromatography, and HRMS (see S4
Supporting Information) and spectral analysis confirmed
that the pure compound obtained was the six-coordinate
dihydrido complex PV meso-triphenylcorrole 7 and not the
1
reduced PIII complex (Scheme 3). The H NMR spectrum
of 7 showed four doublets at 8.72, 8.93. 9.02 and 9.22 ppm
corresponding to eight β-pyrrole protons and a doublet at
–2.70 ppm corresponding to two axial hydride ligands,
which supports the six-coordination environment around
the PV ion in 7 (Figure 5 and inset i). As the hydride ions
are bound directly to the PV ion, strong P–H coupling with
a coupling constant J of ca. 935 Hz was observed, which is
in agreement with the literature data.[12b] The proton-de-
coupled 31P NMR spectrum of 7 (Figure 5, inset ii) showed
a signal at –251 ppm consistent with six-coordination for
the PV ion. The absorption spectrum of 7 recorded in
CH2Cl2 (see S9, Supporting Information) showed four Q-
bands, which are bathochromically shifted compared to
those of 6. Furthermore, the Soret band in 7 is split and is
bathochromically shifted compared to that of 6. Electro-
chemical studies of 7 showed one reversible oxidation at
Figure 4. (a) Comparison of Q-band spectra of 1 (dotted line) in
dry CH2Cl2 and 6 (solid line) in CH3OH recorded at room tem-
perature. The corresponding Soret band comparison is shown as
inset. Concentrations of solution used for Soret band and Q-band
measurements were 10–6 and 10–5 m, respectively. (b) Comparison
of normalized fluorescence spectra of 1 (dotted line) in dry CH2Cl2
and 6 (solid line) in CH3OH recorded at room temperature.
The electrochemical properties of 1 were studied by cyclic 0.51 V, two irreversible oxidations at 1.06 and 1.18 V and
voltammetry and differential pulse voltammetry in dry one reversible reduction at 1.33 V (see S10, Supporting In-
CH2Cl2 in the presence of a trace amount of TFA by using formation). Compared to six-coordinate 6, compound 7 is
a saturated calomel electrode (SCE) as the reference elec-
trode and tetrabutylammonium perchlorate as the support-
ing electrolyte. Six-coordinate 6 showed one reversible oxi-
dation, two irreversible oxidations and one reversible re-
duction. However, five-coordinate 1 showed one irreversible
and one quasireversible oxidation but did not show any re-
duction (see S7, Supporting Information). The oxidation
potentials of 1 were almost the same as that of 6 (Table 1),
which indicates that 1 is as electron-rich as 6.
The fluorescence properties of 1 and 6 were studied by
both steady-state and time-resolved fluorescence tech-
niques. A comparison of the steady-state fluorescence spec-
tra of 1 and 6 is shown in Figure 4 (b). It is established that
corroles containing main group elements are more fluores-
Figure 5. Partial 1H NMR spectrum of 7 recorded in CDCl3 at
cent than transition metallocorroles, and AlIII and GaIII
room temperature. The insets show (i) signal for the axial hydrogen
atom coupled with the central phosphorus and (ii) 31P NMR spec-
metallocorroles are the brightest corrole complexes re-
ported.[6] Our earlier fluorescence study on six coordinate trum of 7.
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easier to oxidize and reduce. The decrease in the HOMO– average P–N bond length (ca. 1.80 Å) found in 2 but is
LUMO gap from 2.13 V in 6 to 1.83 V in 7 is in agreement slightly shorter than the average P–N bond length (1.83 Å)
with the observed redshifts in the absorption bands of 7 observed in 6. However, the average P–N bond length found
compared to those of 6. The fluorescence band of 7 is also in PV corrole complexes 1, 2 and 6 is somewhat shorter than
significantly bathochromically shifted (ca. 100 nm) com- that of analogous PV porphyrin complexes (average P–N
pared to that of 6 (see S11, Supporting Information). How- distance 1.89 Å)[19] as well as the average M–N distances
ever, the fluorescence yield of 7 is reduced compared to that found in metal complexes of meso-triaryl corroles.[3,4]
of 6. Thus, 7 exhibited interesting spectral and electrochem- Furthermore, the crystal structure of 1 revealed that the
ical properties similar to other PV meso-triarylcorroles.
plane of the corrole ring is distorted and has a domelike
structure. This is because, 1 is five coordinate and the cen-
tral phosphorus ion is pulled towards the axial O atom
causing a strain in the corrole skeleton, which results in
distortion of the corrole ring. However, the corrole ring in
Crystallographic Characterization
Further proof for the five-coordination of 1 was provided six-coordinate 6 is more planar than that in free base cor-
by single-crystal X-ray crystallography, and ORTEP plots role[20] as well as in other metallocorroles.[21] In free base
of 1 are presented in Figure 6. Compound 1 was crystallized corroles, such as 5,10,15-triphenylcorrole, the three inner
by the slow diffusion of n-hexane into a dry dichlorometh- NH protons cause steric crowding inside the corrole ring,
ane/chloroform mixture in the presence of a trace amount which results in the distortion of the corrole macrocycle.
of TFA over one week. The structure of 1 obtained here is On complexation with the small PV ion, the strain imposed
compared with our earlier reported six-coordinate PV cor- by the inner NH protons is released and the corrole ring
role 6[13] and the previously reported five-coordinate PV becomes more planar in six-coordinate 6. Furthermore, in
corrole 2, which contains an axial –OH group.[12a] Unlike
6, which crystallized in orthorhombic space group P21, 1
crystallized in the monoclinic space group P21/n. The crys-
tal data and data collection parameters for 6 and 1 are sum-
marized in Table 2. To the best of our knowledge, 1 is the
first PV=O complex of meso-triarylcorrole characterized by
single-crystal X-ray analysis. In 1, the five-coordinate phos-
phorus ion is 0.456 Å out of the mean corrole plane
towards the axial oxygen atom (Table 1). This is similar to
what is observed in the crystal structure of 2, in which the
central phosphorus ion was displaced by ca. 0.41 Å out of
the mean corrole plane towards the axial –OH group. Such
out of plane displacement of the central atom of me-
talloporphyrins[17] or metallocorroles[2,18] is commonly ob-
served for five-coordinate complexes but not for six-coordi-
nate complexes. For example, in six-coordinate 6, the cen-
tral phosphorus ion is almost in the mean plane defined by
the four nitrogen atoms of the pyrrole rings. Similarly, in
the case of the six-coordinate PV complex of 5,10,15,20-
tetraphenylporphyrin,[19] which is a close analogue of six-
coordinate 6, the central phosphorus atom has negligible
out-of-plane displacement (ca. 0.09 Å) from the mean plane
of the pyrrole nitrogen atoms. Furthermore, in 1, the P=O
bond length is 1.50 Å, which is slightly shorter than the P–
OH bond length of ca. 1.532 Å observed in 2. Similarly, the
P–O bond lengths (P–O1 1.668, P–O2 1.663 Å) observed in
6 are somewhat longer than those in 1. The P=O bond
length in 1 is much shorter than the P–O bond lengths ob-
served in other analogues such as six-coordinate PV meso-
tetraarylporphyrin complexes.[19] All of these observations
support the hypothesis that the oxygen atom is bound to
the central phosphorus ion through a double bond in 1,
unlike other PV complexes of porphyrins and related macro-
cycles, in which the phosphorus ion is bound to the axial
oxygen atom through a single bond. The four P–N bond
lengths are not equivalent in 1; the average P–N bond
Figure 6. ORTEP diagram of 1: a) perspective view, b) side view
and c) top view (the TFA molecule is omitted for clarity). Ellipsoids
length (ca. 1.80 Å) is almost in the same range of the are drawn at 50% probability level.
6
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A Five-Coordinate Oxophosphorus(V) meso-Triphenylcorrole
six-coordinate 6, the opposite meso-phenyl groups are ori- interesting properties. Currently, the reactivity of five- and
ented in a mutually opposite direction, whereas in five-co- six-coordinate PV meso-triarylcorroles complexes is under
ordinate 1, the opposite phenyl groups are oriented in the investigation.
same direction, and the average dihedral angles of the op-
posite meso-phenyl groups are ca. 55° and ca. 56°. The
Experimental Section
other meso-phenyl group is almost perpendicular (dihedral
angle ca. 90°) to the mean plane of the corrole ring in both
1 and 6. Interestingly, 1 was crystallized along with a TFA
molecule, which is bound to the P=O oxygen atom through
strong hydrogen bonding (CF3COO–H3a···O1=P1) as
shown in Figure 6 (a). If the hydrogen bonding and the
TFA molecule are not considered, the PV corrole 1 is quite
symmetric with a mirror plane going through the phos-
phorus ion, the meso carbon atom (C20) and the phenyl
ring attached to the meso carbon atom (C20).
Chemicals: All general chemicals and solvents were procured from
S. D. Fine Chemicals, India. Column chromatography was per-
formed with silica gel and basic alumina obtained from Sisco Re-
search Laboratories, India. Tetrabutylammonium perchlorate was
purchased from Fluka and used without further purification. All
NMR solvents were used as received. Solvents such as dichloro-
methane, tetrahydrofuran (THF) and n-hexane were purified and
distilled by standard procedures.
Instrumentation: The 1H and 31P{1H} NMR (δ in ppm) spectra
were recorded with a Bruker AVANCE III 400 MHz spectrometer.
Tetramethylsilane (TMS) was used as an internal reference for H
1
Table 2. Crystallographic data for compounds 1 and 6.
NMR spectra (residual proton; δ = 7.26 ppm) in CDCl3 and 85%
H3PO4 was used as an external reference for 31P NMR spectra in
CDCl3 and CD3OD. The HRMS spectra were recorded with a Q-
Tof micromass spectrometer. Absorption and steady state fluores-
cence spectra were obtained with Perkin–Elmer Lambda-35 and
PC1 Photon Counting Spectrofluorometer manufactured by ISS
U.S.A., respectively. The fluorescence quantum yields (Φ) of PV
meso-triaryl corroles 1 and 6 were estimated from the emission and
absorption spectra by the comparative method[22] using tetraphen-
ylporphyrin (H2TPP) as the standard (Φ = 0.11). The time-resolved
fluorescence decay measurements were carried out at the magic an-
gle by using a picosecond-diode-laser-based time-correlated single-
photon-counting (TCSPC) fluorescence spectrometer from IBH,
UK. All decay curves were fitted to single exponential functions by
using IBH software. Cyclic voltammetry (CV) and differential pulse
voltammetry (DPV) studies were carried out with a BAS electro-
chemical system by utilizing the three-electrode configuration con-
sisting of glassy carbon (working electrode), platinum wire (auxil-
iary electrode) and saturated calomel (reference electrode) elec-
trodes. The experiments were performed in dry CH3OH and
CH2Cl2 with 0.1 m tetrabutylammonium perchlorate as the sup-
porting electrolyte.
[P(TPC)O] (1)
[P(TPC)(OCH3)2] (6)
Molecular formula
Fw
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C39H24F3N4O3P
685.59
monoclinic
P21/n
18.368(6)
7.992(3)
22.098(7)
90
101.640(7)
90
3177.2(18)
4
0.152
1.431
C39H29N4O2P
616.64
orthorhombic
P21
8.3816(4)
9.5266(6)
37.694(2)
90
90
90
3009.8(3)
8
0.136
γ [°]
V [Å3]
Z
μ [mm–1]
Dcalcd. [mgm–3]
F(000)
1.361
1288
1408
2θ range [°]
1.88–25.03
5600 [R(int) = 0.0862]
0.0572, 0.1301
0.1216, 0.1660
0.994
3.28–25.00
22842/5261
0.0445, 0.0844
0.0684, 0.0895
0.929
e data (Rint
)
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
GOF
Largest diff. peak/
0.448/–0.629
0.241/–0.208
hole [eÅ–3]
X-ray Crystallography: A single crystal of suitable size for X-ray
diffractometry was selected under a microscope and mounted on
the tip of a glass fibre, which was positioned on a copper pin.
The X-ray data for 1 was collected with a Bruker Kappa CCD
diffractometer, employing graphite-monochromated Mo-Kα radia-
tion at 200 K and the θ–2θ scan mode. The space group for 1 was
determined on the basis of systematic absences and intensity statis-
tics, and the structure of 1 was solved by direct methods using
SIR92 or SIR97 and refined with SHELXL-97.[23] An empirical
absorption correction by multiscans was applied. All non-hydrogen
atoms were refined with anisotropic displacement factors. Hydro-
gen atoms were placed in ideal positions and fixed with relative
isotropic displacement parameters. Selected crystallographic data
for 1 are given in Table 2.
Conclusions
We isolated a stable five-coordinate PV=O complex of
meso-triphenylcorrole [P(TPC)O] by treating the six-coordi-
nate PV complex [P(TPC)(OH)2] in CH2Cl2 with TFA at
room temperature followed by recrystallization. The struc-
ture of [P(TPC)O] is unambiguously confirmed by X-ray
crystallography. The corrole ring in [P(TPC)O] is slightly
distorted and the phosphorus ion is placed above the cor-
role plane by 0.456 Å, unlike the six-coordinate complex
[P(TPC)(OCH3)2], in which the corrole ring is planar and
the PV ion is almost in the N4 plane of the corrole ring. The
absorption, electrochemical and fluorescence properties of
[P(TPC)O] are very interesting and distinct compared to
those of six-coordinate PV corrole complexes. [P(TPC)O] is
highly fluorescent with a respectable quantum yield (Φ) and
singlet state lifetime (τ). The treatment of [P(TPC)O] with
LiAlH4 resulted in the formation of six-coordinate (5,10,15-
CCDC-870321 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
General Synthesis: Free base meso-5,10,15-triphenylcorrole
(H3TPC) was synthesized by following a literature method.[15] The
phosphorus derivatives 5 and 6 of corroles were synthesized as pre-
triphenylcorrole)dihydridophosphorus(V), which possesses viously reported.[13]
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: I20651
/KAP1
Date: 02-08-12 17:12:36
Pages: 10
A. Ghosh, W.-Z. Lee, M. Ravikanth
FULL PAPER
[2]
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Compound 1: To
a
dichloromethane (50 mL) solution of
(5,10,15-triphenylcorrole)dihydroxyphosphorus(V) (5) (100 mg,
0.169 mmol), TFA (130 μL, 1.696 mmol) was added dropwise, and
the reaction mixture was stirred for 30 min in air. The deep pink-
violet solution immediately turned red. The progress of the reaction
was followed by TLC analysis and absorption spectroscopy. After
completion of the reaction, the solvent was evaporated under re-
duced pressure with a rotary evaporator. The crude solid was
recrystallized from dry CH2Cl2/dry n-hexane and afforded a pur-
ple-red solid in quantitative yield (95 mg, 0.166 mmol). 1H NMR
(400 MHz, CDCl3): δ = 9.47 (br., 2 H, β-pyrrole H), 9.25 (br., 2 H,
β-pyrrole H), 9.22 (br., 2 H, β-pyrrole H), 8.94 (br., 2 H, β-pyrrole
H), 8.43 (br., 1 H, Ar), 8.25–8.27 (br. m, 4 H, Ar), 7.73–7.85 (br.
m, 10 H, Ar) ppm. 31P{1H} NMR (400 MHz, CDCl3): δ =
–98.5 ppm. UV/Vis (CH2Cl2): λmax (logε) = 405 (5.40), 447 (3.74),
482 (sh), 522 (4.08), 557 (4.28) nm. HRMS: m/z = 571.1688 [M +
1]+. C37H23N4OP·CF3COOH: calcd. C 68.36, H 3.50, N 8.18;
found C 68.59, H 3.25, N 8.57.
[3]
Compound 7: To a stirred dry diethyl ether solution (80 mL) of 1
(100 mg, 0.175 mmol), LiAlH4 (67 mg, 1.75 mmol) was added un-
der a nitrogen atmosphere. The reaction mixture was heated to re-
flux for 20 min under a nitrogen atmosphere. As the reaction pro-
gressed, the reaction mixture changed from pink-red to green and
finally to greenish violet. The excess LiAlH4 was quenched by add-
ing methanol and water to the reaction mixture at low temperature.
The reaction mixture was filtered, and the filtrate was evaporated
with a rotary evaporator under reduced pressure. The crude solid
was loaded on a basic alumina column and the desired first green-
ish-violet band was collected by using dichloromethane/petroleum
ether (7:3). The compound was recrystallized from dichlorometh-
ane/n-hexane and afforded pure crystalline 7 as a dark violet solid
in 58% yield (57 mg, 0.102 mmol). 1H NMR (400 MHz, CDCl3):
3
3
δ = 9.22 [d, JH,H = 4.24 Hz, 2 H, β-pyrrole H], 9.02 [d, JH,H
=
4.84 Hz, 2 H, β-pyrrole H], 8.93 [d, 3JH,H = 4.16 Hz, 2 H, β-pyrrole
3
H], 8.73 [d, JH,H = 4.80 Hz, 2 H, β-pyrrole H], 8.27–8.29 (m, 4 H,
Ar), 8.17–8.20 (m, 2 H, Ar), 7.72–7.81 (m, 9 H, Ar), –2.70 [d, JP,H
= 934.94 Hz, 2 H, axial H] ppm. 31P{1H} NMR (400 MHz,
CDCl3): δ = –251.01 ppm. UV/Vis (CH2Cl2): λmax (logε) = 320 (br.,
4.37), 422 (sh), 431 (4.97), 456 (5.08), 542 (br., 3.72), 588 (3.55),
635 (br., 3.96), 689 (4.59) nm. HRMS: m/z = 556.1819 [M]+.
C37H25N4P (556.61): calcd. C 79.77, H 4.49, N 10.06; found C
79.35, H 4.15, N 10.34.
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M. R. thanks the Department of Atomic Energy, Government of
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and Industrial Research (CSIR), India for a fellowship.
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Received: June 14, 2012
Published Online: ᭿
Eur. J. Inorg. Chem. 0000, 0–0
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www.eurjic.org
9

Job/Unit: I20651
/KAP1
Date: 02-08-12 17:12:36
Pages: 10
A. Ghosh, W.-Z. Lee, M. Ravikanth
FULL PAPER
Phosphorus complexes
A. Ghosh, W.-Z. Lee,
M. Ravikanth* ................................ 1–10
A stable five-coordinate PV=O complex of
meso-triphenylcorrole was isolated and
structurally characterized, and its proper-
ties were studied.
Synthesis, Structure and Properties of a
Five-Coordinate Oxophosphorus(V) meso-
Triphenylcorrole
Keywords: Fluorescence / Phosphorus / Co-
ordination modes / Corroles
10
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