TY - JOUR
T1 - A kinetic study of photosubstitution of carbon monoxide and triphenylphosphine in complexes Mn(η
5
-CH
3
C
5
H
4
)(CO)
3-n
(PPh
3
)
n
(n = 0, 1 and 2)
AU - Teixeira, Gabriela
AU - Avilés, Teresa
AU - Dias, Alberto R.
AU - Pina, Fernando
PY - 1988/9/20
Y1 - 1988/9/20
N2 -
The kinetics of photosubstitution of carbon monoxide and triphenylphosphine in complexes Mn(η
5
-CH
3
C
5
H
4
)(CO)
3-n
(P(C
6
H
5
)
3
)
n
(n = 0, 1, 2) have been studied at an irradiation wavelength of 366 nm. The kinetics of the reaction occurring upon the irradiation of Mn(η
5
-CH
3
C
5
H
4
)(CO)
3
(A), in the presence of PPh
3
in n-hexane are consistent with the following reaction sequence: {A figure is presented}. The quantum yields for the carbon monoxide substitution by PPh
3
are 0.77 ± 0.05 and 0.59 ± 0.05 for derivatives A and B, respectively. In the case of C no replacement of the ligand carbon monoxide was observed. With B, the triphenylphosphine ligand was not replaced by CO, but with C the replacement took place with a quantum yield of 0.88 ± 0.05. The ratio between rate constants for the recombination reactions, i.e. of the intermediate Mn(η
5
-CH
3
C
5
H
4
)(CO)
2
with CO, (K
1
) or with PPh
3
, (K
2
), is K
1
/K
2
0.5 The analogous ratio for the intermediate Mn(η
5
-CH
3
C
5
H
5
)(CO)PPh
3
with CO (K
3
) or with PPh
3
(K
4
) is K
3
/K
4
3.5.
AB -
The kinetics of photosubstitution of carbon monoxide and triphenylphosphine in complexes Mn(η
5
-CH
3
C
5
H
4
)(CO)
3-n
(P(C
6
H
5
)
3
)
n
(n = 0, 1, 2) have been studied at an irradiation wavelength of 366 nm. The kinetics of the reaction occurring upon the irradiation of Mn(η
5
-CH
3
C
5
H
4
)(CO)
3
(A), in the presence of PPh
3
in n-hexane are consistent with the following reaction sequence: {A figure is presented}. The quantum yields for the carbon monoxide substitution by PPh
3
are 0.77 ± 0.05 and 0.59 ± 0.05 for derivatives A and B, respectively. In the case of C no replacement of the ligand carbon monoxide was observed. With B, the triphenylphosphine ligand was not replaced by CO, but with C the replacement took place with a quantum yield of 0.88 ± 0.05. The ratio between rate constants for the recombination reactions, i.e. of the intermediate Mn(η
5
-CH
3
C
5
H
4
)(CO)
2
with CO, (K
1
) or with PPh
3
, (K
2
), is K
1
/K
2
0.5 The analogous ratio for the intermediate Mn(η
5
-CH
3
C
5
H
5
)(CO)PPh
3
with CO (K
3
) or with PPh
3
(K
4
) is K
3
/K
4
3.5.
UR - http://www.scopus.com/inward/record.url?scp=0011457741&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(88)80302-4
DO - 10.1016/0022-328X(88)80302-4
M3 - Article
AN - SCOPUS:0011457741
SN - 0022-328X
VL - 353
SP - 83
EP - 91
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -