O-alkylation of dihydroxo(tetraarylporphyrinato)phosphorus(V) and antimony(V) complexes with alkyl halides

Article abstract of DOI:10.1246/bcsj.75.1757

The O-alkylation of dihydroxo(tetraarylporphyrinato)phosphorus(V) complexes with several kinds of alkyl bromide in MeCN in the presence of K₂CO₃ and 18-crown-6 ether produced dialkoxo(tetraarylporphyrinato)phosphorus(V) complexes in-

Full text of DOI:10.1246/bcsj.75.1757

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 1757–1760 (2002) 1757
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
O-Alkylation of Dihydroxo(tetraarylporphyrinato)phosphorus(Ⅴ) and
Antimony(Ⅴ) Complexes with Alkyl Halides
Alkylation of Dihydroxo(porphyrinato)metal
Y. Andou et al.
Yoshito Andou, Kazuki Ishikawa, Kensuke Shima, Tsutomu Shiragami,* Masahide Yasuda, and
02
57
Haruo Inoue
60
Department of Applied Chemistry, Faculty of Engineering, Miyazaki University, and CREST, JST(Japan Science and
Technology), Gakuen-Kibanadai, Miyazaki 889-2192
SJA8
09-2673
340
(Received September 25, 2001)
01
02
.3
The O-alkylation of dihydroxo(tetraarylporphyrinato)phosphorus(Ⅴ) complexes with several kinds of alkyl bro-
mide in MeCN in the presence of K2CO3 and 18-crown-6 ether produced dialkoxo(tetraarylporphyrinato)phosphorus(Ⅴ)
complexes in-moderate-good yields. Similar O-alkylation was applied to dihydroxo(tetraarylporphyrinato)antimony(Ⅴ)
complexes. The O-alkylation proceeded by the occurrence of an SN2 attack of the alkoxide anion of the complexes at the
carbon substituted with halides.
Porphyrinatometal complexes are chemically and biologi-
cally important molecules that have versatile catalytic capabil-
ities in an electron-transfer reaction or energy transfer.1 There-
fore, a number of porphyrinatometal complexes have been syn-
thesized.2 Our interests have been paid to high-valent porphy-
rinatophosphorus(Ⅴ) and antimony(Ⅴ) complexes having a va-
riety of axial ligands from the standpoints of the photoelec-
tronic properties, redox electrochemistry, and catalytic activi-
ties.3,4 However, convenient methods to introduce axial
ligands to the porphyrinatoantimony or phosphorus complexes
have rarely been reported.
The synthesis of dialkoxo-coordinated tetraarylporphyri-
natophosphorus(Ⅴ) and antimony(Ⅴ) complexes ([M(TAP)-
(OR)2]; M = P and Sb, TAP = tetraarylporphyrinato group)
can be achieved by a substitution reaction of [M(TAP)Br2]
with ROH or an alkylation reaction of [M(TAP)(OH)2] with
RX (X = halide, tosylate etc.). However, the yields of the re-
action of [M(TAP)Br2] with ROH have usually been low.
Segawa and Shimidzu have preliminarily reported the O-alky-
lation of dihydroxo(tetraphenylporphyrinato)phosphorus ([P-
(TPP)(OH)2]; TPP = tetraphenylporphyrinato group) with
alkyl halides (RX).5 In order to develop a convenient and effi-
cient method to prepare [M(TAP)(OR)2] (M = P and Sb), we
investigated the scope and limitation of the O-alkylation of
[M(TAP)(OH)2] complexes with RX.
Result and Discussion
As the starting materials, we used dihydroxo(tetraarylporph-
rinato)phosphorus(Ⅴ) and antimony(Ⅴ) hexafluorophosphate
complex ([P(TMP)(OH)2] and [M(TPP)(OH)2]; M = P and Sb,
TMP
= tetra(p-methoxyphenyl)porphyrinato group, see
Scheme 1), which could be easily prepared by the hydrolysis
of [P(TMP)Cl2], [P(TPP)Cl2] and [Sb(TPP)Br2], respective-
ly.5,6 Shimidzu and co-workers’ method involved the O-alkyl-
ation of [P(TPP)(OH)2] with RX (R = Me, Et), having good
leaving groups (X = I, OSO2C6H4Me, OSO2CF3), which oc-
curred in DMF in the presence of K2CO3 at room temperature.5
We investigated the O-alkylations of [M(TAP)(OH)2] (M = P
and Sb) using RX (X = Br and Cl), which are the more avail-
able alkyl reagents.
In attempts to find the optimum conditions, control experi-
ments were performed for the O-alkylation of [P(TMP)(OH)2]
Scheme 1.

1758 Bull. Chem. Soc. Jpn., 75, No. 8 (2002)
Alkylation of Dihydroxo(porphyrinato)metal
(0.02 mmol) with n-PrX (X = Cl, Br, and I; 10–100 mmol) in
the presence of K2CO3 (0.06 mmol) and 18-crown-6 ether
(0.03 mmol) in the solvent (50 mL) under refluxing conditions.
As alkylating agents, although n-PrBr and n-PrI were effective,
n-PrCl was ineffective. Therefore, we used RBr as alkyl re-
agents because of easy handling and more available reagents.
O-alkylation at room temperature required a longer reaction
time. K2CO3/18-crown-6 was used as a base, because of the
occurrence of a relatively clean reaction compared with the
cases of other bases (e.g. pyridine, Et3N, and NaH). It was
found that MeCN and THF were better solvents, since O-alky-
lation with n-PrBr proceeded effectively. DMF was a poor sol-
vent because of the occurrence of demetallation from the por-
phyrin complex, although Segawa et al. succeeded to carry out
O-alkylation in DMF at room temperature.5 Probably K2CO3
served as a stronger base under refluxing conditions to lead the
demetallation. Therefore, O-alkylations were performed in
MeCN in the presence of K2CO3/18-crown-6 under refluxing
conditions throughout the present investigation.
alkoxo complex, [Sb(TPP)(OH)(OR)]. The O-alkylation of
[Sb(TPP)(OH)2] with tertiary RX (e.g. t-BuBr) did not occur
due to the steric hindrance.
An alternative synthetic method7 of [Sb(TPP)(OR)2] was at-
tempted by the reaction of [Sb(TPP)Br2] with ROH. However,
the reaction of [Sb(TPP)Br2] with ROH under refluxing condi-
tions gave a mono-alkoxo complex, [Sb(TPP)(OR)Br]. For
example, the reaction of [Sb(TPP)Br2]+Br− with EtOH gave
[Sb(TPP)(OEt)Br]+Br− (4; 95%).
In conclusion, the optimum route to [M(TAP)(OR)2] (M =
P and Sb) is the double O-alkylation of [M(TAP)(OH)2] (M =
P and Sb) with RBr under basic conditions. The present meth-
od will be applied to porphyrinatophosphorus and antimony
complexes having various functionalized axial ligands.
Experimental
1H NMR spectra were taken in CDCl3 using tetramethylsilane
as an internal standard on a Bruker AC 250P spectrometer at 250
MHz. UV spectra were measured on a Hitachi U2001 spectrome-
ter. SIMS were obtained on a Hitachi M2000A spectrometer.
High-resolution FAB-MS were obtained on a JEOL JMS-HX
110A spectrometer using m-nitrobenzyl alcohol as a matrix agent.
Materials. Reagents were obtained from the following sourc-
es: antimony(Ⅲ) bromide, chloroform, acetonitrile, potassium car-
bonate, propyl bromide, isopropyl bromide, and butyl bromide
from Nacalai Tesque; anhydrous pyridine, dichloromethane, hex-
ane, methanol, hydrobromic acid, tetrahydrofurane, 18-crown-6
ether, butyl chloride, butyl iodide, propyl iodide, and 1,4-dibro-
mobutane from Wako Pure Chemical Industries; tetraphenylpor-
phyrin, t-butyl bromide, 3-bromo-1,1,1-trifluoropropane, benzyl
bromide, and 1,3-dibromopropane from Tokyo Kasei; N,N-di-
methylformamide from Katayama Kagaku; silver hexafluorophos-
phate, phosphoryl chloride, and tetra(4-methoxyphenyl)porphyrin
from Aldrich.
General Procedure of O-Alkylation. A dry MeCN solution
(50 mL) containing RX (1 mL; 10–100 mmol), [M(TAP)(OH)2]
(M = P or Sb; 0.02 mmol),5,6 K2CO3 (0.06 mmol), and 18-crown-
6 (0.03 mmol) was refluxed at 85 °C under a nitrogen atmosphere.
The mixture was cooled, filtered, and concentrated in vacuo. A
dichloromethane solution of the crude product was added into
hexane to form the precipitate. The dichloromethane solution of
the precipitate was washed three times with 50 mL portions of
H2O. After removing the solvent, the crude product was subjected
to the column chromatography on silica gel (Fuji-Silysia FL60D)
to give [M(TAP)(OR)2].
The reaction progress from [M(TAP)(OH)2] to
[M(TAP)(OR)2] (1 (M = P) and 2 (M = Sb)) was followed by
spectral changes of a Soret band of [M(TAP)(OH)2]: λmax
=
440 nm for [P(TMP)(OH)2], 424 nm for [P(TPP)(OH)2], and
417 nm for [Sb(TPP)(OH)2]. The structures of 1 and 2 were
certainly confirmed by observing common up-field shifts of all
protons on the alkyl group in the 1H NMR spectra.
Although the O-alkylation of [P(TMP)(OH)2] with i-PrBr
gave 1b, that with i-PrI did not at all, probably because an
elimination of HI from i-PrI occurred predominantly. RCl
were unreactive, except for the case of PhCH2Cl. In the cases
of RBr (R = CH2wCH–CH2–, Br(CH2)3–, and CH3(CH2)3–)
and PhCH2Cl, the O-alkylation products (1c–e and 1f) were
obtained. A small amount of free base porphyrin (H2TMP)
was formed as a by-product, except for the case of entry 9.
The O-alkylation of [P(TPP)(OH)2] with RBr (R = Et, n-Pr,
and CH2wCH–CH2–) and PhCH2Cl gave [P(TPP)(OR)2] (1g-i
and 1m) in moderate-to-good yields. The O-alkylation of
[P(TPP)(OH)2] with CH3(CH2)nBr (n = 5, 7, 9) smoothly gave
1j–l irrespective of the long alkyl chain. No O-alkylation with
t-BuBr, HOCH2CH2Br, NCCH2CH2Br, and CF3CH2CH2Br oc-
curred at all. The present method was applied to the O-alkyla-
tion of [Sb(TPP)(OH)2] with RBr (R = n-Bu, i-Pr, CH2wCH–
CH2–, Br(CH2)3–) and PhCH2Cl, which gave [Sb(TPP)(OR)2]
(2a–d) in moderate-to-good yields, except for entry 24. In the
case of i-PrBr (entry 24), a mono-alkylated complex,
[Sb(TPP)(OH)(O-i-Pr)] (3), was formed without the formation
of [Sb(TPP)(O-i-Pr)2]. The O-alkylation of [Sb(TPP)(OH)2]
with i-PrI, t-BuBr, BrCH2CH2Br, NCCH2CH2Br, and
CF3CH2CH2Br gave little or no products. The results are sum-
marized in Table 1.
Dipropoxo[tetra(4-methoxyphenyl)porphyrinato]phospho-
rus(Ⅴ) Hexafluorophosphate (1a). UV–vis λmax/nm (log ε) 441
1
(5.46), 566 (4.08), 612 (3.87); H NMR δ −2.48 (4H, dt, JP-H
=
11.4, J = 5.7 Hz, CH2), −1.50 (4H, m, CH2), −1.15 (6H, t, J =
7.4 Hz, CH3), 4.04 (12H, s, OMe), 7.32 (8H, d, J = 8.6 Hz, Ph),
7.88 (8H, d, J = 8.6 Hz, Ph), 9.05 (8H, d, JP-H = 2.7 Hz, pyrrole).
HRMS (FAB) Found: m/z 881.3468. Calcd for C54H50N4O6P: M+,
881.3468. Anal. Calcd for C54H50N4O6P2F6•C6H14: C 64.74; H,
5.80; N, 5.03%. Found: C, 63.84; H, 6.15; N, 4.25%.
Diisopropoxo[tetra(4-methoxyphenyl)porphyrinato]phos-
phorus(Ⅴ) Hexafluorophosphate (1b). UV–vis λmax/nm (log ε)
441 (5.46), 566 (4.08), 612 (3.87); SIMS m/z 881 (M+); 1H NMR
δ −2.8 – −2.5 (2H, m, CH), −2.25– −2.23 (12H, m, CH3), 4.03
(12H, s, OCH3), 7.30 (8H, d, J = 8.7 Hz, Ph), 7.89 (8H, d, J = 8.7
Hz, Ph), 9.06 (8H, d, JP-H = 2.8 Hz, pyrrole).
The pKa values of [M(TAP)(OH)2] were determined based
on the spectral change by the addition of KOH: pKa = 10.0 for
[P(TMP)(OH)2], pKa = 9.5 for [P(TPP)(OH)2], and pKa =
10.3 for [Sb(TPP)(OH)2]. Therefore, the axial hydroxy group
of [P(TMP)(OH)2], [P(TPP)(OH)2], and [Sb(TPP)(OH)2] can
be readily dissociated by K2CO3. O-Alkylation proceeded by
the occurrence of an SN2 attack of [M(TAP)(OH)O−] at the
carbon substituted with halides. In the case of a secondary RX
(e.g. i-PrBr), the SN2 attack would be slow to give a mono-
Bis(allyloxo)[tetra(4-methoxyphenyl)porphyrinato]phos-

Y. Andou et al.
Bull. Chem. Soc. Jpn., 75, No. 8 (2002) 1759
Table 1. O-Alkylation of [M(TAP)(OH)2](M = P and Sb) with RXa)
Entry
M
Yb)
R
X
Solvent
Product
(Yield/%)
1
2
3
4
5
6
7
8
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
H
H
H
H
H
H
H
H
H
n-Pr
n-Pr
n-Pr
n-Pr
n-Pr
i-Pr
i-Pr
CH2wCHCH2–
Br(CH2)3–
CH3(CH2)5–
PhCH2–
Et
I
MeCN
MeCN
MeCN
THFc)
DMFd)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
1a (73)
1a (0)
1a (93)
1a (96)
1a (0)
Cl
Br
Br
Br
Br
I
1b (91)
1b (0)
Br
Br
Br
Cl
Br
Br
Br
Br
Br
Br
Cl
Br
Cl
Br
Br
Cl
Br
1c (65)
1d (100)
1e (33)
1f (77)
1g (74)f)
1h (91)
1i (82)
1j (24)
1k (75)
1l (52)
1m (96)
2a (73)
2a (0)
9
10
11
12e)
13
14
15
16
17
18
19
20
21
22
23
24
n-Pr
CH2wCHCH2–
CH3(CH2)5–
CH3(CH2)7–
CH3(CH2)9–
PhCH2–
n-Bu
P
P
Sb
Sb
Sb
Sb
Sb
Sb
n-Bu
H
H
H
H
CH2wCHCH2–
Br(CH2)3–
PhCH2–
i-Pr
2b (86)
2c (43)
2d (47)
3
(11)g)
a) All reaction was carried out for the solution (50 mL) containing [M(TAP)(OH)2]
(0.02 mmol), RX (10–100 mmol), K2CO3 (0.06 mmol), and 18-crown-6 (0.03 mmol) at
refluxing temperature for 24 h. b) p-Substituents on the aryl group of the porphyrin ring
(p-Y–C6H4–; Y = OMe and H). c) Tetrahydrofuran. d) N,N-Dimethylformamide.
e) Reaction for 27 h. f) O-Alkylation of [P(TPP)(OH)2]+Cl− with EtI in the presence of
K2CO3 in DMF at room temperature gave 1g in 76% yield. See Ref. 5. g) Isolated as
[Sb(TPP)(OH)(O-i -Pr)] (3).
phorus(Ⅴ) Hexafluorophosphate (1c). UV–vis λmax/nm (log ε)
441 (5.46), 566 (4.08), 612 (3.87); SIMS m/z 877 (M+); 1H NMR
δ −1.77 (4H, m, CH2), 2.61–3.65 (6H, m, CHwCH2), 4.03 (12H,
s, OCH3), 7.30 (8H, d, J = 8.7 Hz, Ph), 7.87 (8H, d, J = 8.7 Hz,
Ph), 9.06 (8H, d, JP-H = 2.8 Hz, pyrrole). Anal. Calcd for
C54H46N4O6P2F6•C6H14: C, 64.98; H, 5.45; N, 5.05%. Found: C,
64.83; H, 5.58; N, 4.62%.
δ −1.26 (4H, d, JP-H = 9.90 Hz, CH2), 4.02 (12H, s, OCH3), 4.60
(4H, d, J = 7.3 Hz, Ph), 6.39–6.62 (6H, m, Ph), 7.23 (8H, d, J =
8.7 Hz, Ph), 7.61 (8H, d, J = 8.7 Hz, Ph), 9.05 (8H, d, JP-H = 3.0
Hz, pyrrole).
Diethoxo(tetraphenylporphyrinato)phosphorus(Ⅴ) Hexa-
fluorophosphate (1g). UV–vis λmax/nm (log ε) 423 (5.39), 554
(4.12), 597 (3.79); SIMS m/z 733 (M+); 1H NMR δ −2.29–
−2.37 (4H, dt, JP-H = 12.6, J = 6.3 Hz, CH2), −1.74 (6H, t, J =
6.3 Hz, CH3), 7.74–7.79 (12H, m, Ph), 7.96 (8H, d, J = 6.5 Hz,
Ph), 9.06 (8H, d, JP-H = 2.9 Hz, pyrrole). Anal. Calcd for
C48H38N4O2P2F6: C 65.60; H, 4.36; N, 6.38%. Found: C, 66.22; H,
4.50; N, 6.36%.
Dipropoxo(tetraphenylporphyrinato)phosphorus(Ⅴ) Hexa-
fluorophosphate (1h). UV–vis λmax/nm (log ε) 423 (5.40), 555
(4.10), 598 (3.80); SIMS m/z 761 (M+); 1H NMR δ −2.48 (4H, dt,
JP-H = 12.6, J = 6.3 Hz, CH2), −1.48 (4H, m, CH2), −1.13 (6H, t,
J = 6.3 Hz, CH3), 7.79–7.97 (20H, m, Ph), 9.07 (8H, d, JP-H = 2.8
Hz, pyrrole).
Bis(3-bromopropoxo)[tetra(4-methoxyphenyl)porphyrina-
to]phosphorus(Ⅴ) Hexafluorophosphate (1d).
UV–vis λmax/
nm (log ε) 441 (5.46), 566 (4.08), 612 (3.87); SIMS m/z 1039
1
(M+); H NMR δ −2.24 (4H, dt, JP-H = 12.6, J = 6.3 Hz, CH2),
−0.99 (4H, quint, J = 6.3 Hz, CH2), 1.20 (4H, t, J = 6.3 Hz,
CH2Br), 4.03 (12H, s, OCH3), 7.30 (8H, d, J = 8.7 Hz, Ph), 7.91
(8H, d, J = 8.7 Hz, Ph), 9.06 (8H, d, JP-H = 2.7 Hz, pyrrole).
Bis(hexyloxo)[tetra(4-methoxyphenyl)porphyrinato]phos-
phorus(Ⅴ) Hexafluorophosphate (1e). UV–vis λmax/nm (log ε)
441 (5.46), 566 (4.10), 612 (3.88); SIMS m/z 965 (M+); 1H NMR
δ −2.46 (4H, dt, JP-H = 15.0, J = 7.5 Hz, CH2), −1.57 (4H, quint,
J = 7.5 Hz, CH2), −0.91 (4H, quint, J = 7.5 Hz, CH2), −0.09
(4H, quint, J = 7.5 Hz, CH2), 0.35 (10H, m, CH2 and CH3), 4.05
(12H, s, OCH3), 7.33 (8H, d, J = 8.7 Hz, Ph), 7.89 (8H, d, J = 8.7
Hz, Ph), 9.08 (8H, d, JP-H = 2.9 Hz, pyrrole).
Bis(allyloxo)(tetraphenylporphyrinato)phosphorus(Ⅴ)
Hexafluorophosphate (1i). UV–vis λmax/nm (log ε) 423 (5.43),
554 (4.09), 602 (3.83); 1H NMR δ −1.78 (4H, m, CH2), 2.65–3.65
(6H, m, CHwCH2), 7.77–7.97 (20H, m, Ph), 9.06 (8H, d, JP-H
=
Bis(benzyloxo)[tetra(4-methoxyphenyl)porphyrinato]phos-
phorus(Ⅴ) Hexafluorophosphate (1f). UV–vis λmax/nm (log ε)
440 (5.45), 566 (4.09), 612 (3.90); SIMS m/z 977 (M+); 1H NMR
2.9 Hz, pyrrole). HRMS (FAB) Found: m/z 757.2732. Calcd for
C50H38N4O2P: M+, 757.2732. Anal. Calcd for C50H38N4O2P2F6: C,
66.52; H, 4.24; N, 6.21%. Found: C, 66.44; H, 4.84; N, 5.65%.

1760 Bull. Chem. Soc. Jpn., 75, No. 8 (2002)
Alkylation of Dihydroxo(porphyrinato)metal
Bis(hexyloxo)(tetraphenylporphyrinato)phosphorus(Ⅴ)
m, Ph), 7.94–8.21 (20H, m, Ph), 9.47 (8H, s, pyrrole). Anal. Calcd
for C58H42N4O2PF6Sb•C6H14: C 65.15; H, 4.78; N, 4.75%. Found:
C, 64.80; H, 4.21; N, 5.17%.
Hexafluorophosphate (1j). UV–vis λmax/nm (log ε) 423 (5.43),
1
553 (4.09), 590 (3.88); SIMS m/z 845 (M+); H NMR δ −2.48
(4H, dt, JP-H = 15.0, J = 7.5 Hz, CH2), −1.56 (4H, quint, J = 7.5
Hz, CH2), −0.90 (4H, quint, J = 7.5 Hz, CH2), −0.09 (4H, quint,
J = 7.5 Hz, CH2), 0.30 (10H, m, CH2 and CH3), 7.81–7.97 (20H,
m, Ph), 9.08 (8H, d, JP-H = 2.6 Hz, pyrrole).
Hydroxo(isopropoxo)(tetraphenylporphyrinato)antimo-
ny(Ⅴ) Hexafluorophosphate (3). UV–vis λmax/nm (log ε) 421
1
(5.45), 550 (4.08), 590 (3.90); SIMS m/z 809 and 811 (M+); H
NMR δ −3.32– −3.43 (1H, m, CH), −2.52 (6H, d, J = 6.2 Hz,
–CH3), 7.85-7.94 (12H, m, Ph), 8.22 (4H, d, J = 7.3 Hz, Ph), 8.48
(4H, d, J = 7.3 Hz, Ph), 9.45 (8H, s, pyrrole). Axial hydroxy
Bis(octyloxo)(tetraphenylporphyrinato)phosphorus(Ⅴ)
Hexafluorophosphate (1k). UV–vis λmax/nm (log ε) 423 (5.43),
1
1
555 (4.09), 602 (3.83); SIMS m/z 901 (M+); H NMR δ −2.48
group was not observed in H NMR spectra. Anal. Calcd for
(4H, dt, JP-H = 15.2, J = 7.6 Hz, CH2), −1.56 (4H, quint, J = 7.6
Hz, CH2), −0.90 (4H, quint, J = 7.6 Hz, CH2), −0.08 (4H, quint,
J = 7.6 Hz, CH2), 0.36 (4H, quint, J = 7.6 Hz, CH2), 0.60–0.83
(14H, m, CH2 and CH3), 7.81–7.97 (20H, m, Ph), 9.08 (8H, d, JP-H
= 2.5 Hz, pyrrole).
C47H36N4O2PF6Sb: C 59.08; H, 3.80; N, 5.86%. Found: C, 60.29;
H, 3.71; N, 5.82%.
Bromo(ethoxo)(tetraphenylporphyrinato)antimony(Ⅴ)
Hexafluorophosphate (4). UV–vis λmax/nm (log ε) 424 (5.33),
557 (3.98), 596 (3.75); 1H NMR δ −2.29 (3H, quint, J = 6.9 Hz,
–CH3), −2.18 (2H, t, J = 6.9 Hz, –CH2), 7.90–8.00 (12H, m, Ph),
8.31 (4H, d, J = 6.6 Hz, Ph), 8.38 (4H, d, J = 6.6 Hz, Ph), 9.56
(8H, s, pyrrole). HRMS (FAB) Found: m/z 857.0876. Calcd for
C46H33BrN4OSb: M+, 859.0872. Anal. Calcd for C46H33BrN4-
OSbPF6•C6H14: C, 57.27; H, 4.34; N, 5.14%. Found: C, 56.38; H,
4.00; N, 5.33%.
Bis(decyloxo)(tetraphenylporphyrinato)phosphorus(Ⅴ)
Hexafluorophosphate (1l). UV–vis λmax/nm (log ε) 423 (5.43),
1
553 (4.10), 598 (3.87); SIMS m/z 957 (M+); H NMR δ −2.48
(4H, dt, JP-H = 15.0, J = 7.5 Hz, CH2), −1.56 (4H, quint, J = 7.5
Hz, CH2), −0.91 (4H, quint, J = 7.5 Hz, –CH2–), −0.07 (4H,
quint, J = 7.5 Hz, CH2), 0.36 (4H, quint, J = 7.5 Hz, CH2), 0.64
(4H, quint, J = 7.5 Hz, CH2), 0.73–1.12 (18H, m, CH2 and CH3),
7.81–7.88 (20H, m, Ph), 9.08 (8H, d, JP-H = 2.3 Hz, pyrrole).
Bis(benzyloxo)(tetraphenylporphyrinato)phosphorus(Ⅴ)
References
Hexafluorophosphate (1m). UV–vis
λmax/nm (log ε) 423
1
a) F. R. Hopf and D. G. Whitten, “Porphyrins and Metal-
1
(5.40), 555 (4.05), 600 (3.84); SIMS m/z 857 (M+); H NMR δ
−1.30 (4H, d, JP-H = 9.90 Hz, CH2), 4.63 (4H, d, J = 7.3 Hz, Ph),
6.41–6.64 (6H, m, Ph), 7.69–7.77 (20H, m, Ph), 9.07 (8H, d, JP-H
= 2.9 Hz, pyrrole).
loporphyrins,” ed by K. M. Smith, Elsevier, New York (1975), p.
667, and references cited therein. b) K. Kalyanasundaram and M.
Grätzel, “Photosensitization and Photocatalysis Using Inorganic
and Organometallic Compounds,” Kluwer Academic Publishers,
Amsterdam (1993).
Dibutoxo(tetraphenylporphyrinato)antimony(Ⅴ) Hexafluo-
rophosphate (2a). UV–vis λmax/nm (log ε) 419 (5.42), 550
(4.11), 590 (3.85); 1H NMR δ −2.58 (4H, t, J = 6.0 Hz, CH2),
−1.95 (4H, quint, CH2), −1.62 – −1.52 (4H, m, CH2), −0.60
(6H, t, J = 6.0 Hz, CH3), 7.95–8.35 (20H, m, Ph), 9.54 (8H, s,
pyrrole). HRMS (FAB) Found: m/z 879.2659. Calcd for
C52H46N4O2Sb: M+, 879.2659. Anal. Calcd for C52H46N4O2-
PF6Sb•2C6H14: C, 64.16; H, 6.23; N, 4.68%. Found: C, 63.57; H,
6.28; N, 4.14%.
2
a) M. R. Wasielewski, Chem. Rev., 92, 435 (1992). b) S.
Anderson, H. L. Anderson, and J. K. M. Sanders, Acc. Chem. Res.,
26, 469 (1993).
3
a) T. Vangberg and A. Ghosh, J. Am Chem. Soc., 121,
12154 (1999). b) L. Giribabu, T. A. Rao, and B. G. Maiya, Inorg.
Chem., 38, 4971 (1999). c) K. Hirakawa and H. Segawa, J. Photo-
chem. Photobiol. A: Chem., 123, 67 (1999). d) Y. Yamamoto and
K. Akiba, J. Organomet. Chem., 611, 200 (2000). e) H.
Yamaguchi, M. Kamachi, and A. Harada, Angew. Chem., Int. Ed.,
2000, 3829. f) T. Ogawa, H. Furuta, M. Takahashi, A. Morino,
and H. Uno, J. Organomet. Chem., 611, 551 (2000).
Bis(allyloxo)(tetraphenylporphyrinato)antimony(Ⅴ) Hexa-
fluorophosphate (2b). UV–vis λmax/nm (log ε) 420 (5.34), 551
(3.96), 591 (3.72); SIMS m/z 847 and 849 (M+); H NMR δ −
1
1.72 (4H, dt, J = 3.1, 1.6 Hz, CH2), 2.50 (2H, quint, J = 1.6 Hz,
CHw), 3.25–3.68 (4H, m, wCH2), 7.91–8.33 (20H, m, Ph), 9.55
(8H, s, pyrrole). Anal. Calcd for C50H38N4O2PF6Sb•C6H14: C,
62.29; H, 4.85; N, 5.19%. Found: C, 63.27; H, 4.19; N, 5.78%.
Bis(3-bromopropoxo)(tetraphenylporphyrinato)antimo-
ny(Ⅴ) Hexafluorophosphate (2c). UV–vis λmax/nm (log ε) 419
4
a) S. Takagi, T. Okamoto, T. Shiragami, and H. Inoue, J.
Org. Chem., 24, 7373 (1994). b) T. Okamoto, S. Takagi, T.
Shiragami, and H. Inoue, Chem. Lett., 1993, 687. c) T. Shiragami,
K. Kubomura, D. Ishibashi, and H. Inoue, J. Am. Chem. Soc., 118,
6311 (1996). d) S. Takagi, M. Suzuki, T. Shiragami, and H. Inoue,
J. Am. Chem. Soc., 119, 8712 (1997).
1
(5.67), 551 (4.28), 590 (4.03); SIMS m/z 1009 (M+); H NMR δ
5
K. Kunimoto, H. Segawa, and T. Shimidzu, Tetrahedron
−2.54 (4H, t, J = 5.5 Hz, CH2), −1.08 (4H, quint, J = 5.5 Hz,
CH2), 0.63 (4H, t, J = 5.5 Hz, CH2), 7.89–8.38 (20H, m, Ph), 9.53
(8H, s, pyrrole).
Lett., 33, 6327 (1992).
6
H. Inoue, T. Okamoto, Y. Kameo, M. Sumitani, A.
Fujiwara, D. Ishibashi, and M. Hida, J. Chem. Soc., Perkin Trans.
1, 1994, 105.
Bis(benzyloxo)(tetraphenylporphyrinato)antimony(Ⅴ)
Hexafluorophosphate (2d). UV–vis λmax/nm (log ε) 420 (5.33),
7
T. Barbour, W. J. Belcher, P. J. Brothers, C. E. F. Rickard,
1
550 (3.98), 591 (3.75); SIMS m/z 947 and 949 (M+); H NMR δ
and D. C. Ware, Inorg. Chem., 31, 746 (1992).
−1.10 (4H, s, CH2), 3.67 (4H, d, J = 7.5 Hz, Ph), 6.32–6.70 (6H,