Highly active, air-stable palladium catalysts for the C-C and C-S bond-forming reactions of vinyl and aryl chlorides: use of commercially available [(t-Bu)(2)P(OH)](2)PdCl(2), [(t-Bu)(2)P(OH)PdCl(2)](2), and [[(t-Bu)(2)PO...H...OP(t-Bu)(2)]PdCl](2) as catalysts.