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Esters and amides were mechanochemically prepared by palladium-catalyzed carbonylative reactions of aryl iodides by using molybdenum hexacarbonyl as a convenient solid carbonyl source and avoiding a direct handling of gaseous carbon monoxide. Real-time monitoring of the mechanochemical reaction by in situ pressure sensing revealed that CO is rapidly transferred from Mo(CO) 6 to the active catalytic system without significant release of molecular carbon monoxide., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)