The use of weakly coordinating anions BAr4F (where Ar-F = 3,5-(CF3)(2)C6H3) and CB11H12 allows one to access clean reactions of the [(PNP)Pd](+) fragment (PNP = bis(2-(Pr2P)-Pr-i (4) over bar -Me-phenyl)amido) with the B-H bond in cate-cholborane (CatBH) and catecholdiboron (CatBBCat). In both cases, a net heterolytic cleavage of B H or B B takes place, fragment. The resultant products [(PN(BCat)P)PdH](+) (2) with the nitrogen atom of PNP being a recipient of a boryl and [(PN(BCat)P)PdBCat](+) (3) were isolated as either BAr4F or CB,,H,2 salts and fully characterized. They are susceptible to hydrolysis, with the B-N bond hydrolyzing selectively and rapidly at RT to give [(PN(H)P)PdH](+) (1) and [(PN(H)P)- PdBCat](+) (4). Notably, 4 and 2 are isomers, but they do not interconvert even under thermolysis at 90 degrees C. The Pd-B bond in 4 can be further hydrolyzed more slowly, to give 1. On the other hand, a Pd-B bond was formed from the Pd-H bond in 2 by reaction with excess CatBH (and evolution of H-2), producing 3.