*3.1. Methods and Materials*

Infrared spectra were recorded in diffuse reflectance mode using a Fourier-transform infrared spectrometer FTIR Nicolet 6700 (Thermo Fisher Scientific, Waltham, MA, USA; (scan range 400–4000 cm−<sup>1</sup> , 64 scans, 4 cm−<sup>1</sup> resolution). The samples analyzed in this study were diluted with KBr (grade for spectroscopy) before the measurement. Nuclear magnetic resonance (NMR) spectra were recorded at 25 ◦C on a Varian UNITY Inova 400 spectrometer (Palo Alto, CA, USA) operating at 399.95, 100.58 and 376.29 MHz for <sup>1</sup>H, <sup>13</sup>C and <sup>19</sup>F, respectively. Chemical shifts (δ in ppm) are expressed relative to internal tetramethylsilane (1H and <sup>13</sup>C) and to external neat CFCl<sup>3</sup> ( <sup>19</sup>F). GC analyses were performed with an Agilent 6850 gas chromatograph (Santa Clara, CA, USA) equipped with a DB-5 column (0.18 mm diameter, 50 m length).

Elemental composition of the deposited catalysts was determined using the standard combustion method and a PerkinElmer PE 2400 CHN analyzer (Waltham, MA, USA). The content of palladium in solid samples and in the reaction mixtures was determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) on an IRIS Interpid II instrument (Thermo Electron, Waltham, MA, USA) with axial plasma and ultrasonic CETAC nebulizer U-5000AT+. The samples were dissolved in a mixture of HF with HNO<sup>3</sup> (3:2, suprapure from Merck; Kenilworth, NJ, USA) at 50 ◦C for 15 min and evaporated. The residue was diluted with redistilled water for <sup>105</sup>Pd (the wavelength used for the spectrophotometric analysis was 324.270 nm).

Dichloromethane was dried over potassium carbonate and distilled under argon. Other solvents were dried over activated 3 Å molecular sieves. Triethylamine was dried over sodium metal and distilled. Other chemicals were used as obtained from commercial sources (Sigma-Aldrich, St. Louis, MO, USA). Materials **2–7** were prepared as previously described [29]. The analytical data determined for the newly prepared samples are as follows. The IR spectra were identical to those of the authentic samples.

Elemental analysis for **2**: C 6.3, N 1.1, S 0.95 mmol·g −1 . Elemental analysis for **3**: C 7.0, N 1.9 mmol·g −1 . Elemental analysis for **4**: C 11.3, N 1.1, P 0.77 mmol·g −1 . Elemental analysis for **5**: C 7.0, N 0.97, S 0.52, Pd 0.64 mmol·g −1 . Elemental analysis for **6**: C 7.6, N 1.7, Pd 0.62 mmol·g −1 . Elemental analysis for **7**: C 11.3, N 1.1, P 0.21, Pd 0.43 mmol·g −1 .

Catalyst **8** was prepared similarly by direct palladation of material **1**. Thus, palladium(II) acetate (0.449 g, 2.0 mmol) dissolved in dry dichloromethane (10 mL) was added to a suspension of support **1** (2.0 g) [29] in the same solvent (50 mL). After stirring the resulting mixture at room temperature for 1 h, the solid was filtered off and washed with dichloromethane until the washings were colorless. Then, the filter cake was washed a few more times (2-3×) and left to dry in the air.

Characterization data for **8**. IR (DRIFTS): 3648 w, 3243 br w, 1567 m, 1430 w, 1388 w, 1330 vw, 1080 s (Si-O-Si asymetric stretch), 944 vw, 794 m (Si-O-Si symetric stretch), 688 w, 462 (Si-O-Si bending) cm−<sup>1</sup> . Elemental analysis: C 6.1, N 1.1, Pd 0.58 mmol·g −1 .
