S1 Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2009. Supplementary Information Alkynylation of Aryl Halides with Perfluoro-Tagged Palladium Nanoparticles Immobilized on Silica Gel under Aerobic, Copper-, and Phosphine-Free Conditions in Water Roberta Bernini, a Sandro Cacchi, b* Giancarlo Fabrizi, b Giovanni Forte, c Francesco Petrucci, c Alessandro Prastaro, a Sandra Niembro, d Alexandr Shafir, d Adelina Vallribera d a Dipartimento A.B.A.C., Università della Tuscia e Consorzio Universitario “La Chimica per l’Ambiente”, Via S. Camillo De Lellis, 01100 Viterbo, Italy. b Dipartimento di Chimica e Tecnologia del Farmaco Università degli Studi “La Sapienza”, P.le A. Moro 5, 00185 Rome, Italy. b Istituto Superiore di Sanità, Viale Regina Elena 299, 00161 Rome, Italy. d Department of Chemistry, Universitat Autònoma de Barcelona, Cerdanyola 08193, Spain. E-mail: sandro.cacchi@uniroma1.it Experimental Section General Information Melting points were determined with a Büchi B-545 apparatus and are uncorrected. 1-ethynyl-4- benzonitrile, 1-ethynyl-4-methoxybenzene and 1-ethynyl-4-acetophenone were prepared from the corresponding aryl iodides and trimethylsilylacetylene according to literature (Mori, A. et al., J. Org. Chem., 2000, 65, 1780). The other reagents and solvents are commercially available and were used as purchased, without further purification. Compounds were purified on axially compressed columns, packed with SiO 2 25-40 µm (Macherey Nagel), connected to a Gilson solvent delivery system and to a Gilson refractive index detector, and eluting with n-hexane/AcOEt mixtures. 1 H NMR (400.13 MHz) and 13 C NMR (100.6 MHz) spectra were recorded with a Bruker Avance 400 spectrometer. Infrared (IR) spectra were recorded on a JASCO FT/IR-430 spectrophotometer. Mass spectra were determined with a Shimadzu QP2010 Gas Chromatograph Mass spectrometer (EI ion source). Determination of Pd at mass 105 was performed by means of a sector field inductively coupled plasma mass spectrometry technique (SF-ICP-MS, Thermo-Fischer, Bremen, Germany) in medium resolution (m/∆m=3000) to avoid that interferent signals coming from molecular species, i.e., 40 Ar 65 Cu, could overlap the signal of Pd at the chosen mass and overestimate the actual Pd value. Quantification of Pd was carried out through the external calibration curve. Rhodium (Rh), selected