The reactions of so called "tuck-in" permethyl zirconocene compounds Cp*(eta(5)-eta(1)-C5Me4CH2)ZrX (X = Cl (1a), C6H5 (1b), CH3 (1c)) with the highly electrophilic boranes HB(C6F5)(2) and B(C6F5)(3) are described. The products are zwitterionic olefin polymerization catalysts. Reactions with la and Ib yielded single products cleanly, but reactions with tuck-in methyl starting material Ic gave mixtures. Spectroscopic and structural studies showed that the electrophilic zirconium center in the product zwitterions was stabilized by a variety of mechanisms. In the products of reaction between 1a and 1b with HB(C6F5)(2), Cp*[eta(5) eta(1)-C5Me4CH2B(C6F5)(2)(mu-H)]ZrX (X = Cl (2a), 74%), C6H5 (2b, 62%)), the metal is chelated by a pendant hydridoborate moiety. Chloride product 2a was characterized crystallographically. In the reaction of B(C6F5)(3) with 1a, the fluxional zwitterionic product Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrCl (3a, 84%) is stabilized by a weak donor interaction between one of the ortho fluorine atoms of the -CH2B-(C6F5)(3) counterion and the zirconium center (Zr-F = 2.267(5) Angstrom). In the product of the reaction between 1b and B(C6F5)(3), Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrC6H5 (3b, 82%), a similar ortho-fluorine interaction was found in a yellow kinetic product (y-3b), which converted upon heating gently to a thermodynamic orange polymorph (o-3b) in which the zirconium center is compensated via an agostic interaction from an ortho C-H bond of the phenyl group and an interaction between the methylene group of the -CH2B-(C6F5)(3) counteranion. These compounds were both characterized by X-ray crystallography. Zwitterion o-3b reacts with H2 to form the zwitterionic hydride Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrH (4, 77%), characterized by NMR spectroscopy and X-ray crystallography to reveal a return to the ortho-fluorine mode of stabilization. Compounds 2a, 3a, o-3b, and 4 were all found to be active ethylene polymerization catalysts; the chloride derivatives required minimal amounts of methylaluminoxane (MAO) to alkylate the zirconium center. Polymerization data are discussed in light of the structural findings for the catalysts employed.