Mechanistic studies on the B(C(6)F(5))(3) catalyzed allylstannation of isomeric substituted benzaldehydes are reported. Confirming a report by Maruoka et al., good (5:1) to excellent (>20:1) selectivities for ortho over para isomers are observed when 1:1 mixtures (X = OMe, Cl, F, OTBS) are allylstannated with C(3)H(5)SnBu(3) in the presence of B(C(6)F(5))(3) (2.5% per CHO). The best selectivities are observed for the anisaldehydes. Multinuclear NMR studies on solutions of B(C(6)F(5))(3) and C(3)H(5)SnBu(3) (1:1 to 1:5) show that the borane abstracts the allyl group from the organotin reagent, forming an adduct (C(6)F(5))(3)B...CH(2)CHCH(2)SnBu(3), 1, or ion pair [(C(6)F(5))(3)BCH(2)CH=CH(2)](-)[Bu(3)SnCH(2)CHCH(2)SnBu(3)](+), 2, depending on the reagent ratio. These compounds are important in the mechanism of Lewis acid catalyzed 1,3-isomerization of substituted allyl stannanes. When allyltin reagent is added to solutions of B(C(6)F(5))(3) and ortho-anisaldehyde (1:5) at -60 degrees C, conversion to the stannylium ion pair [Bu(3)Sn(ortho-anisaldehyde)(2)](+)[o-ArCH(allyl)OB(C(6)F(5))(3)](-), o,o-4, is observed. The structure of this species was confirmed by (1)H, (11)B, (19)F, and (119)Sn NMR spectroscopy and by forming related ion pairs (o-5 and o,o-5) utilizing the [B(C(6)F(5))(4)](-) counteranion via reaction of [Bu(3)Sn](+)[B(C(6)F(5))(4)](-) with aldehyde. The anion in o,o-4 is formed via direct allylation of the ortho-anisaldehyde/B(C(6)F(5))(3) adduct o-3, while the cation arises upon aldehyde ligation of the resulting tributylstannylium ion. The crystal structure of the related derivative ortho-C(6)H(4)(OMe)CHO x SnMe(3)BF(4), 6, showed that the aldehyde binds the tin nucleus only through the carbonyl oxygen. Similar reactions using para-anisaldehyde show that formation of p,p-4 occurs at a much slower rate, again demonstrating the preference for the ortho substituted substrates. For similar experiments using benzophenone, however, formation of the ion pair [Bu(3)Sn(Ph(2)CO)(2)](+)[(C(3)H(5))B(C(6)F(5))(3)](-), 8, was observed, illustrating the differences subtle changes in substrate can bring. Ion pair 8 is formed via the trapping of 1 by the benzophenone substrate. In the presence of excess aldehyde and allyltin reagent, ion pair o,o-4 catalyzes the allylstannation of aldehyde to give the product stannyl ether. Several lines of experimental evidence suggest this is the true catalyst in the system. The chemoselectivity observed thus does not rely on classical chelation control in any way. Rather, we propose that the ortho donor group stabilizes the developing positive charge at the beta carbon of the allyl group and the tin atom during the allylation event. This stabilization renders the ortho substituted substrates kinetically favored toward allylation irrespective of the Lewis acid employed.