Silica-bonded S-sulfonic acid (SBSSA) was prepared by the reaction of 3-mercaptopropylsilica (MPS) and chlorosulfonic acid in tert-butylmethyl ether, and used as a catalyst for the silylation of hydroxyl groups. A good range of primary, secondary alcohols and phenolic hydroxyl groups were effectively converted into their corresponding trimethylsilyl ethers with hexamethyldisilazane (HMDS) in the presence of catalytic amounts of SBSSA under mild conditions at room temperature with short reaction times and in good-to-excellent yields. An excellent chemoselective silylation of hydroxyl groups in the presence of other functional groups was also observed. The heterogeneous catalyst was recycled for 30 runs upon the reaction of benzyl alcohol with HMDS without lossing its catalytic activity.

Heterobimetallic compounds [(C^N)LMePt(μ-O)ReO] (C^N = ppy, L = PPh, 2a; C^N = ppy, L = PMePh, 2b; C^N = bhq, L = PPh, 2c; C^N = bhq, L = PMePh, 2d) containing a discrete unsupported Pt(iv)-O-Re(vii) bridge have been synthesized through a targeted synthesis route. The compounds have been prepared by a single-pot synthesis in which the Pt(iv) precursor [PtMeI(C^N)L] complexes are allowed to react easily with AgReO in which the iodide ligand of the starting Pt(iv) complex is replaced by an ReO anion. In these Pt-O-Re complexes, the Pt(iv) centers have an octahedral geometry, completed by a cyclometalated bidentate ligand (C^N), two methyl groups and a phosphine ligand, while the Re(vii) centers have a tetrahedral geometry. Elemental analysis, single crystal X-ray diffraction analysis and multinuclear NMR spectroscopy are used to establish their identities. The new complexes exhibit phosphorescence emission in the solid and solution states at 298 and 77 K, which is an uncommon property of platinum complexes with an oxidation state of +4. According to DFT calculations, we found that this emission behavior in the new complexes originates from ligand centered LC (C^N) character with a slight amount of metal to ligand charge transfer (MLCT). The solid-state emission data of the corresponding cycloplatinated(iv) precursor complexes [PtMeI(C^N)L], 1a-1d, pointed out that the replacement of I by an ReO anion helps enhancing the emission efficiency besides shifting the emission wavelengths.