Clusteri metaloxidici in

cataliza
Cioloboc Daniela
An !!! !B
Sinteza de clusteri metaloxidici cu propritetati
catalitice si studiul mecanismelor de reactie ale
acestora
- Compusi care prezinta aplicabilitate:
-CataIiza
-ChemIuminiscenta si eIectroIuminsicenta
-Prezinta proprietati antiviraIe si antitumoraIe
-Prietenosi cu mediul
- Stabili in majoriatea starilor de oxidare
- Aproape orice proprietate care are impact asupra
reactivitatii lor poate fi modificata
ecanisme
o(VI)=O]
+4
+ S => o(IV) + SO
o(IV) - 2e
-
=> o(VI)
(ex.: sulfit reductaze)
Citocromul P450
oxigenaze non-heminice
ecanisme
Yamase, T., Catalysis Survey from Asia, 2003, 203-217
o(V)
Sinteza si caracterizarea clusterilor metaloxidici
a
2
CO
3
a
2
oO
4
|P
2
W
18
O
62
]
6
|P
2
W
1S
O
S6
]
12
|P
2
No
2
W
1S
O
61
]
10
200 000 800 600 400
d
b


T
(
%
)
Wavenumber (cm
-1
)
a
c
[1]
Spectrele FT-R ale
K
6
[P
2
W
18
O
62
]xH
2
O (a),
K
10
[P
2
o
2
W
15
O
61
]18H
2
O (b),
K
7
[Cr(H
2
O)P
2
o
2
W
15
O
61
]17H
2
O (c)
i K
16
[Ce(P
2
o
2
W
15
O
61
)
2
]34H
2
O (d)
[1] A.R. Toma, D. Cioloboc, A.. Todea,
L. urean, V. Pacalu, . Rusu,
Studia Universitatis Babe-Bolyai, Seria
Chemia, 2009, ', 33
0
0.5
1
1.5
2
2.5
3
230 330 430 530 630 730
aveIength
a
b
s
o
r
b
a
n
c
e
polioxo
polioxo+ascorbat+
peroxid
polioxo+ascorbat+
peroxid (12h)
tape preliminare ale studiilor
catalitice
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
580 630 680 730 780
aveIength
a
b
s
o
r
b
a
n
c
e
ecanisme propuse, si speciitinta
1. [o(V)=O]
+4
+ S => o(V) + SO ?
Sau
1. [o(V)=O]
+4
+ S => o(V) +
.
SO
-
?
2. o(V) - 2e
-
=> o(V) ?
Sau
2. o(V) - e- => o(V) ?
3. o(V) - e- => o(V) ?
1. Fe() + HO
2
-
=> Fe()-OOH
2. Fe()-OOH + S => SO+Fe()-OH
sau
2. Fe()-OOH +H
+
=> Fe(V)=O + H
2
O
3. Fe(V)=O + S => SO+Fe()
Fe, Cu, Cr, Ce
1. Fe() + e- => Fe()
2. Fe() + O
2
=> Fe()-O
2
3. Fe()-O
2
+ e- => Fe()-OO
2-
4. Fe()-OO
2-
+ H+ => Fe()-OOH
1. Fe() + e- => Fe()
2. Fe() + H
2
O
2
=> Fe()-O
2
2-
3. Fe()-O
2
2-
+ H
+
=> Fe()-OOH
4. Fe()-OOH +H
+
=> Fe(V)=O + H
2
O
xperimente propuse
1. Sinteza si caracterizare compusi (Fe, Co, Cu)
2. Cataliza (chimic, sau electrocataliza)
3. Reducere complex: ascorbat, ditionit, sulfoxilat
4. Reactie forma oxidata cu substrat (aldehide, alcooli, terpene, azotit)
5. Reactie forma oxidata cu peroxid, superoxid
6. Reactie forma redusa cu substrat
7. Reactie forma redusa cu oxidant (O
2
, H
2
O
2
, etc)
etode:
UV-vis, RES, R, R, stopped-flow
'ehnologie noua utilizata in studii
uItumesc pentru atentie!