The stoichiometric and catalytic activations of alkyl halides and acid chlorides by the unsatured Pd-3(dPPM)(3)(CO)(2+) cluster (Pd-3(2+)) are investigated in detail. A series of alkyl halides (R-X; R = t-Bu, Et, Pr, Bu, allyl; X = Cl, Br, I) react slowly with Pd-3(2+) to form the corresponding Pd3(X)(+) adduct and "R+". This activation can proceed much faster if it is electrochemically induced via the formation of the paramagnetic species Pd-3(+). The latter is the first confidently identified paramagnetic Pd cluster. The kinetic constants extracted from the evolution of the UV-vis spectra for the thermal activation, as well as the amount of electricity to bring the activation to completion for the electrochemically induced reactions, correlate the relative C-X bond strength and the steric factors. The highly reactive "R+" species has been trapped using phenol to afford the corresponding ether. On the other hand, the acid chlorides react rapidly with Pd32+ where no induction is necessary. The analysis of the cyclic voltammograms (CV) establishes that a dissociative mechanism operates (RCOCI --> RCO+ + Cl-; R = t-Bu, Ph) prior to Cl- scavenging by the Pd-3(2+) species. For the other acid chlorides (R = n-C6H13, Me2CH, Et, Me, Pr), a second associative process (Pd-3(2+) + RCOCI --> Pd32+.....Cl(CO)(R)) is seen. Addition of Cu(NCMe)(4)(+) or Ag+ leads to the abstraction of Cl- from Pd-3(Cl)(+) to form Pd-3(2+) and the insoluble MCI materials (M = Cu, Ag) allowing to regenerate the starting unsaturated cluster, where the precipitation of MX drives the reaction. By using a copper anode, the quasi-quantitative catalytic generation of the acylium ion ("RCO+") operates cleanly and rapidly. The trapping of "RCO+" with PF6- or BF4- leads to the corresponding acid fluorides and, with an alcohol (R'OH), to the corresponding ester catalytically, under mild conditions. Attempts were made to trap the key intermediates "Pd-3(Cl)M-+....(+II) (M+ = Cu+, Ag+), which was successfully performed for Pd-3(ClAg)(2+), as characterized by P-31 NMR, IR, and FAB mass spectrometry. During the course of this investigation, the rare case of PF6-hydrolysis has been observed, where the product PF2O2- anion is observed in the complex Pd-3(PF2O2)(+), where the substrate is well-located inside the cavity formed by the dppm-Ph groups above the unsatured face of the Pd-3(2+) center. This work shows that Pd3 2+ is a stronger Lewis acid in CH2Cl2 and THF than AICl(3), Ag+, Cu+, and Tl+.