The neutral, dizinc composition of the PD R Zn2X3 complexes contrasts with our previous report on ethylzinc complexes of PD R H (2-R); we had shown that PD H H (2-H) reacts with either 1 or 2 equivalents of ZnEt2 to give the same complex with the composition PD H ZnEt, while no complex of the composition PD H Zn2Et3 was stable. Furthermore, the nonsymmetrical, unbridged structure of our trihalides contrasts with the numerous reported zinc phenolates in which five-coordinate zinc atoms are bridged by the µ-phenolate and also by another µ-anion, including µ-halides. Next, we prepared cationic complexes with the composition (14), and [PD (14) are NMR equivalent at room temperature. As a monometallic control, we also performed metathesis under the same conditions between P 4-tBu HZnI2 (11) and NaBArF, obtaining a complex with the composition [P 4-tBu HZnI][BArF](16, Scheme 1E). By contrast, simple zinc halides bis(pyrazolyl)methane complexes undergo redistribution to form homoleptic complexes under anion metathesis with sodium tetraphenylborate. Presumably the heteroscorpionate structure of our ligands stabilizes the cationic zinc complex to redistribution.