We have experimentally derived 1695 level-to-level rate constants describing both rovibrationally inelastic collisions and exchange reactions in the A1 ¿u +Li2 + Li system. These molecules possess exceptionally high initial rotational energy, with ji extending from 19 to 96. In support of this work we describe 4818 spectral line locations ranging from j0 = 0 to 112 which represents, to our knowledge, the highest j ever reported for lines observed in the A-X state spectrum of molecular lithium by a large margin. Distributions of reactive rate constants describing final rotational levels of products appear to be statistical and are well-modeled by an a priori expression employing the kinematic constraint proposed by Picconatto et al [1]. For the nonreactive case, we observe the phenomenon of quasiresonant vibration-rotation energy transfer (QVRT) according to the well-characterized [2] rule ¿ j/¿v = ¿4 (4:1) as well as the emergence and dominance of novel QVRT behavior according to ¿ j/¿v = ¿2 (2:1) for ji ¿ 76. A noteworthy feature of this emergence is the apparent coexistence of these competing QVRT phenomenon in the vicinity of j = 80. We explore the dynamical causes for this behavior using QCT simulations of atom-molecule collisions, and numerically fit a LEPS-like interaction potential to experimental data. Our computational findings indicate that adherence to 4:1 or 2:1 QVRT behavior at j = 80 is highly dependent on collision geometry. Simulations also provide further insight into the reaction dynamics.