Reaction of [CpCo(C3F7)(I)(L)], (L = PPh,Me (la), PPhMe, (lb), PMe, (lc), and PPh(OMe), (2)), with PPh(OMe), affords diastereomeric Co-and P-chiral metallophosphinates CpCo(C3F7)(L)(P(0)Ph(OMe)), 4a,b,c and 6, respectively. The solid state structure and relative configuration of the lower Rf diastereomeric phosphinate CpCo(C3F7)(PPh(0Me),)(P(O)Ph(OMe)), 6-2, was determined by X-ray diffraction. RR;SS-6-2 crystallizes in the triclinic system with space group PT(no. 2), with a = 12.928(4) A, b = 14.683(4) A, c = 7.666(2) A, a = 103.50(2)O, p = 101.31(3)", y = 109.50(2)", V = 1272.8(7) A3, Z = 2, and R = 0.036 (R,, = 0.030) for 2867 reflections with I > 3.00a(T). CpCo(C,F,)(I)(PPh(OMe),), 2, reacts with PPh,Me to yield the same Co-and P-chiral phosphinate products as obtained for the reaction of l a with PPh(OMe),, albeit with different optical yields. The product stereochemistry is not accounted for by the established mechanism for transition metal Arbuzov-like dealkylations, which requires formation of a common, ionic intermediate [CpCo(C3F7)(PPh,Me)(PPh(OMe),)]+, 3, via iodide substitution and subsequent nucleophilic attack at carbon. A parallel intramolecular dealkylation pathway is proposed to account for the results.