A mild air-stable catalyst from palladium complex having nitrogen as donor ligand for Si-O bond formation is described. A series of mono and disubstituted silyethers are prepared in near quantitative yield from the catalytic reactions of Pd(TMEDA)Cl-2 (TMEDA: N,N,N-N-tetramethylethylenediamine) with different silanes (such as triphenylsilane, triethylsilane, diphenylsilane and methylphenylsilane) and alcohols. The different isomers of naphthalenenediols on reactions with triethylsilane or with triphenylsilane gets converted to give disubstituted product by catalytic amount of Pd(TMEDA)Cl-2. The advantages and disadvantages of this catalyst over RhCl(PPh3)(3) as catalyst for similar reactions is discussed. The catalytic reaction of RhCI(PPh3)(3) with diphenylsilane in stepwise manner forms Si-O and Si-S bond through reductive coupling with 1,4-naphthoquinone followed by the reaction with benzenethiol. (C) 2003 Elsevier Science B.V. All rights reserved.