title: Mechanistic study of the palladium-phenanthroline catalyzed carbonylation of nitroarenes and amines: palladium-carbonyl intermediates and bifunctional effects.
abstract: Palladium-phenanthroline complexes catalyze both the nitroarene carbonylation reaction and the amine oxidative carbonylation reaction to give, depending on the conditions, carbamates and ureas. There is evidence that the key step in both processes is the amine carbonylation. Here, we show that when the reaction is run in methanol key intermediate compounds have the general formula [Pd(RPhen)(COOMe)(2)] (1) (RPhen = 1,10-phenanthroline or one of its substituted derivatives). The kinetics of the reaction of 1 with toluidine in the presence of a carboxylic or phosphorus acid is first-order with respect to complex, acid, and toluidine. A CO atmosphere is also required for the reaction to proceed. Acid dimerization was shown not to be influential under the concentration conditions examined, but reaction between the acid and toluidine is not negligible and a correction has to be applied. Diphenylphosphinic acid is more effective than any carboxylic acid in promoting this reaction, as also observed under catalytic conditions. A series of equilibria and an irreversible acid-assisted proton transfer explain the observed data. Formation of an adduct between complexes of the kind 1 and CO was spectroscopically observed when RPhen = 2,9-Me(2)Phen. Several analogous complexes were also spectroscopically characterized and the X-ray structure of [Pd(2,9-Me(2)Phen)Cl(2)(CO)] was solved. This shows an asymmetric coordination of the nitrogen ligand. Kinetic measurements were also conducted under catalytic conditions. An Eyring plot shows that the effect of the acidic promoter is to decrease the DeltaS(double dagger) value, whereas no positive effect is observed on DeltaH(double dagger). A temperature-dependent correction for the reaction between the acid and aniline and phenanthroline present under the reaction conditions has to be applied. Comparison of the results obtained under stoichiometric and catalytic conditions strongly supports the view that 1 is involved even in the latter and that the acid is acting as a bifunctional promoter.
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica "Lamberto Malatesta" and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy), Fax: (+39) 025-031-4405.
authors.forename: Fabio
authors.initials: F
authors.lastname: Ragaini
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica "Lamberto Malatesta" and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy), Fax: (+39) 025-031-4405.
authors.forename: Michela
authors.initials: M
authors.lastname: Gasperini
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica "Lamberto Malatesta" and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy), Fax: (+39) 025-031-4405.
authors.forename: Sergio
authors.initials: S
authors.lastname: Cenini
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica "Lamberto Malatesta" and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy), Fax: (+39) 025-031-4405.
authors.forename: Lucia
authors.initials: L
authors.lastname: Arnera
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica "Lamberto Malatesta" and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy), Fax: (+39) 025-031-4405.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Caselli
authors.affiliation: Dipartimento di Chimica Strutturale e Stereochimica Inorganica and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy).|Present address: Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012 Berne (Switzerland).
authors.forename: Piero
authors.initials: P
authors.lastname: Macchi
authors.affiliation: Dipartimento di Chimica Strutturale e Stereochimica Inorganica and ISTM-CNR, Università degli Studi di Milano via Venezian 21, 20133 Milano (Italy).
authors.forename: Nicola
authors.initials: N
authors.lastname: Casati