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Here, we show that when the reaction is run in methanol key intermediate compounds have the general formula [Pd(RPhen)(COOMe)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>) (RPhen=1,10\u2010phenanthroline or one of its substituted derivatives). The kinetics of the reaction of <jats:bold>1<\/jats:bold> with toluidine in the presence of a carboxylic or phosphorus acid is first\u2010order 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\u2010assisted proton transfer explain the observed data. Formation of an adduct between complexes of the kind <jats:bold>1<\/jats:bold> and CO was spectroscopically observed when RPhen=2,9\u2010Me<jats:sub>2<\/jats:sub>Phen. Several analogous complexes were also spectroscopically characterized and the X\u2010ray structure of [Pd(2,9\u2010Me<jats:sub>2<\/jats:sub>Phen)Cl<jats:sub>2<\/jats:sub>(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 \u0394<jats:italic>S<\/jats:italic>\u2009<jats:sup>\u2260<\/jats:sup> value, whereas no positive effect is observed on \u0394<jats:italic>H<\/jats:italic>\u2009<jats:sup>\u2260<\/jats:sup>. A temperature\u2010dependent 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 <jats:bold>1<\/jats:bold> is involved even in the latter and that the acid is acting as a bifunctional promoter.<\/jats:p>","DOI":"10.1002\/chem.200801882","type":"journal-article","created":{"date-parts":[[2009,3,9]],"date-time":"2009-03-09T08:29:03Z","timestamp":1236587343000},"page":"8064-8077","source":"Crossref","is-referenced-by-count":72,"title":["Mechanistic Study of the Palladium\u2013Phenanthroline Catalyzed Carbonylation of Nitroarenes and Amines: Palladium\u2013Carbonyl Intermediates and Bifunctional Effects"],"prefix":"10.1002","volume":"15","author":[{"given":"Fabio","family":"Ragaini","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michela","family":"Gasperini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergio","family":"Cenini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lucia","family":"Arnera","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alessandro","family":"Caselli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Piero","family":"Macchi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicola","family":"Casati","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,8,4]]},"reference":[{"key":"e_1_2_5_1_2","volume-title":"Catalytic Reductive Carbonylation of Organic Nitro Compounds","author":"Cenini S.","year":"1996"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950083f"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(99)00230-1"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200700148"},{"key":"e_1_2_5_5_2","unstructured":"\u00a0"},{"key":"e_1_2_5_6_2","unstructured":"J.\u2005H.Grate D.\u2005R.Hamm D.\u2005H.Valentine U.S. Patent US 4705883 1987;"},{"key":"e_1_2_5_7_2","unstructured":"J.\u2005H.Grate D.\u2005R.Hamm D.\u2005H.Valentine U.S. Patent US 4629804 1986;"},{"key":"e_1_2_5_8_2","unstructured":"J.\u2005H.Grate D.\u2005R.Hamm D.\u2005H.Valentine U.S. Patent US 4600793 1986;"},{"key":"e_1_2_5_9_2","unstructured":"J.\u2005H.Grate D.\u2005R.Hamm D.\u2005H.Valentine U.S. Patent US 4603216 1986."},{"key":"e_1_2_5_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00088a015"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990578l"},{"key":"e_1_2_5_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(00)00311-3"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2005.03.059"},{"key":"e_1_2_5_14_2","unstructured":"\u00a0"},{"key":"e_1_2_5_15_2","first-page":"9","journal-title":"Chem. 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On the other hand if the intermediate formation of aniline is involved a mixture of all possible ureas (undeuterated penta\u2010 and decadeuterated) should be obtained with a composition depending on the nitrobenzene conversion. When we performed a carbonylation under conditions similar to those described in the caption of Figure\u20051 but at 90\u2009\u00b0C and for 30\u2005min using equimolar amounts of [D5]PhNO2and PhNH2as substrates the final urea contained 88.0\u2009% undeuterated and 12.0\u2009% pentadeuterated urea. Considering that the nitrobenzene conversion was 6.4\u2009% this deuteration degree is too high to be accounted for by the deuterated aniline that is liberated in solution and evidences a contribution by a direct carbonylation pathway. 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Thus the composition [(Pd(Neoc))2(\u03bc\u2010CO)(\u03bc\u2010TMB)][TMB] may also be proposed for3\u2009c however the observation of only one set of signals for the trimethylbenzoate anion even at 223\u2005K in the1H\u2005NMR spectrum would imply that a fast exchange between the free and the coordinated trimethylbenzoate anion is occurring which is quite surprising for an anion in a bridging position."},{"key":"e_1_2_5_130_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980315b"},{"key":"e_1_2_5_131_2","unstructured":"[Pd(Neoc)(malonate)] was also synthesized but its very low solubility prevented us from studying its reactivity with CO."},{"key":"e_1_2_5_132_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(01)00700-9"},{"key":"e_1_2_5_133_2","doi-asserted-by":"publisher","DOI":"10.1039\/b303006g"},{"key":"e_1_2_5_134_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39920000333"},{"key":"e_1_2_5_135_2","first-page":"117","volume":"124","author":"De Delice V.","year":"1994","journal-title":"Gazz. 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