Crystal structure of a palladium metallacyclic complex: A key-intermediate in the carbonylation of nitrobenzene to isocyanates and carbamates

The palladium–phenanthroline catalyzed carbonylation of nitroarenes to diarylureas: Effect of chloride and diphenylphosphinic acid

“…A second alternative (path B) involves the formation of a metallacyclic intermediate [29][30][31][32][33]. This can decompose to yield phenylisocyanate, which will be trapped by aniline as in path A.…”

Synthesis and Crystal Structure of a Palladium Metallacyclic Complex: A Key Intermediate in the Carbonylation of Azobenzene to N ‐Phenyl Urethane

“…[5] When the same precursor was treated with azobenzene, instead of nitrobenzene, at room temperature, in the presence of free phen and under a CO pressure of 40 atm., a pale yellow solid, formulated as [(phen)PdC(O)N(Ph)N(Ph)C(O)], was obtained. [5] When the same precursor was treated with azobenzene, instead of nitrobenzene, at room temperature, in the presence of free phen and under a CO pressure of 40 atm., a pale yellow solid, formulated as [(phen)PdC(O)N(Ph)N(Ph)C(O)], was obtained.…”

“…[2,3] Mechanistic studies have been carried out based mainly on either the isolation or the spectroscopic detection of several metallacyclic derivatives, which should be directly involved in the catalytic cycle. [5] In this paper we report the isolation and the complete characterization, both in the solid state and in solution, of is proposed as a ''key-intermediate'' for the carbonylation of azobenzene to N-phenyl urethane. [5] In this paper we report the isolation and the complete characterization, both in the solid state and in solution, of is proposed as a ''key-intermediate'' for the carbonylation of azobenzene to N-phenyl urethane.…”

Cyclopentadienyliron complexes of nitrosobenzene: Preparation, structure and reactivity with olefins

“…A few studies have demonstrated the involvement of various metallacycles incorporating RNO 2 and CO in the deoxygenation process [6][7][8]. Nitrenoid species, free or coordinated, have often been presumed to be intermediates in these reactions [1], but direct evidence for their involvement or the intervention of other reactive intermediates in the reactions is scarce.…”