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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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I
1
I
1
AI -CH3

a b Al-O-CH2CH3
Al CH(CH3)2
a b
Al CH2C(CH3)3

a b Al-0-CH2CH2CH2CI
CH3

Al--CHCO2CH3 b
TPP: - 6.9 (a) [C6D6] T(p-Cl)PP: - 7.0 (a) [C6D6]
TPP: -6.4(a), -3.4(b) [C6D6] T(p-Cl)PP: -6.5 (a), -3.5 (b) [C6D6]
TPP: - 1.3 (a) EtioP: -1.8(a)
TPP: - 1.3 (a), 2.1 (b) EtioP: - 1.8 (a), 2.4 (b)
TPP: - 1.40 (a) [C6D6]
TPP: - 1.60 (a), - 1.4 (b)
TPP: - 1.43 (a), - 1.26 (b), 0.82 (c)
TPP: - 1.57 (a), - 1.91 (b), 2.59 (c)
58
58
40
40
58
59
57
18
138
Aida and Inoue
Table 2. (continued)
Compound
Chemical shifts in <5 (ppm)
Reference
Aluminum phenolates
TPP: 2.6 (a), 5.9 (b, c)
TPP: -0.30 (a), 6.18 (b), 3.42 (c) [C6D6]
74
75
I
(
(H3C)3C H
Al 4 -C(CH3)3
Aluminum carboxylates
I (
a b

Al--C-CH2C(CH3)3
I 4
Al-O-C-
CH3
l|

TPP: -0.35 (a), 6.48 (b), 1.04 (c), 6.21 (d), 170 (e) [C6D6] 75
TPP: - 1.4 (a)
TPP: - 0.7 (a), - 0.8 (b)
TPP: - 1.1 (a)
TPP: 4.5 (a), 6.6 (b), 6.8 (c)
43
40
43
43
Aluminum enolates
b H H
:
1
1
I
,AI-
w d C-H e /
H
b H H
Al-O-C
H3C
bd
/
^( Al-
- /
2
\
SPr
TPP: 4.61 (), 6.53 (b), 6.79 (), 2.36 (d), - 0.04 () [ChD6] 76
TPP: 4.75 (), 6.73 (b), 6.92 (), 3.29 (d), - 0.73 () [C6D6] 77
TPP: - 1.48 (), 2.03 (b), -0.78 () [C6D6]
78
42 / Metalloporhpyrins as Catalysts
139
Table 2. (continued)
Compound Chemical shifts in <5 (ppm)
Reference
Aluminum thiolates and amides
a b
^;ai---s---223 TPP: - 1.42 (a), 0.55 (b), -0.10 (c) [C6D6]
49
a b TPP: 4.58 (a), 6.50 (b), 6.76 (c) [C6D"1
49
H H
|a|-s4^~hC
a b
^>|-N(CH2CH3)2 TPP: - 1.32 (a), - 1.38 (b) [CftD6]
77
TPP: 5.10,15.20-Tetraphc'nylporphinato, T( /)-1)PP: 5.10.15,2()-
Tetrakis(4'-chlorophenyl)poiphinato. EtioP: Etioporphyrinato-I.
Time (min)
Figure 2. Polymerization of epoxyethane (11, R = H) initiated with
chloroaluminum tetraphenylporphyrin (1c) ([11]0/[1c]0 = 400,
[11]0 = 16.7 mM) in CH2CI2 at room temperature. Time course of
polymerization.
high-molecular-weight living polymer (25, R = Me) with an alcoholate
reactive end (Scheme 2B).30 Upon acidic workup, the alcoholate reactive
end (25) is hydrolyzed to release a polymer possessing a terminal
hydroxyl group. Studies on the polymerization mechanism can take great
advantage of a strong shielding effect of the porphyrin ring current
(Table 4), where 'H NMR signals due to the reactive end of the growing
polymer are observed at an upheld region separately from other signals on
the spectrum. For example, the 'FI NMR spectrum of a polymerization
mixture of 1,2-epoxypropane (11, R = Me) with lc in CDC13 shows a set of
characteristic signals at an upfield region, due to Al-OCHMeCHo- (25, R =
Me) (Table 4).30 Upon addition of epoxyethane (11, R = H) to this
mixture, the spectral profile at the upfield region completely changes to
show the appearance of a set of new triplet signals due to
Conversion (%)
Figure 3. Polymerization of epoxyethane (11, R = H) initiated with
chloroaluminum tetraphenylporphyrin (1c) ([11]0/[1c]0 = 400, [11]o = 16.7
mM) in CH2CI2 at room temperature. Relationship between molecular weight
(Mn; O), molecular weight distribution (Mw/Mn; #) and monomer conversion.
Al-OCH2CH2- (26), which is formed as a result of the block
copolymerization of 11 (R = H) from 25 (R = Me) (Scheme 2C)
By virtue of the clear initiation mechanism, well-defined end-
functionalized polyethers can be synthesized. For example, use of an
aluminum porphyrin having a 4-vinylphenolate ligand at the axial position
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