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)

Gabriela Teixeira, Teresa Avilés, Alberto R. Dias, Fernando Pina

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Abstract

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.

Original languageEnglish
Pages (from-to)83-91
Number of pages9
JournalJournal Of Organometallic Chemistry
Volume353
Issue number1
DOIs
Publication statusPublished - 20 Sep 1988

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