Covalent bonding interactions between the Lewis acid and Lewis base functionalities have been probed in a series of "frustrated Lewis pairs" (FLPs) (mainly substituted vinylene linked intramolecular phosphane borane adducts), using solid-state nuclear magnetic resonance techniques and accompanying DFT calculations. Both the B-11 NMR isotropic chemical shifts and nuclear electric quadrupolar coupling parameters turn out to be extremely sensitive experimental probes for such interactions, revealing linear correlations with boron phosphorus internuclear distances. The principal component V-zz of the B-11 electric field gradient tensor is tilted slightly away (similar to 20 degrees) from the boron phosphorus internuclear vector, leading to an improved understanding of the remarkable reactivity of the FLPs. Complementary P-31{H-1}-CPMAS experiments reveal significant P-31-B-11 scalar spin-spin interactions ((1)J approximate to 50 Hz), evidencing covalent bonding interactions between the reaction centers. Finally, B-11{P-31} rotational echo double resonance (REDOR) experiments show systematic deviations from calculated curves based on the internuclear distances from X-ray crystallography. These deviations suggest non-zero contributions from anisotropic indirect spin spin (J anisotropy) interactions, thereby offering additional evidence for covalent bonding.