The J(B-11,B-11) coupling constants of various salts of the electron-precise hexacyanodiborane(6) dianion, [B-2(CN)(6)](2-), were obtained using B-11 double-quantum filtered (DQF) J-resolved solid-state nuclear magnetic resonance (SSNMR) spectroscopy. Our results show that the magnitude of the DQF J splitting is influenced by both the crystallographic symmetry of the system and the presence of dynamics. The :splittings are amplified by a factor of 3 as compared to the corresponding theoretical J coupling constants for cases where (1) there is an absence of dynamics but the boron pairs are crystallographically equivalent or (2) the boron pairs are crystallographically inequivalent but are rendered magnetically equivalent on the time scale of the experiment due to dynamic disorder, which was identified by B-11 and C-13 SSNMR experiments. Consequently, molecular motions-need to-be taken into consideration when interpreting the results of DQF J-resolved experiments, and conversely, these experiments maybe used to identify dynamic disorder. Variable-temperature NMR data support the notion of three different motional processes with correlation times ranging from 10(2) to 10(6) s(-1) over the temperature range of 248-306 K. When molecular motion and crystallographic symmetry are both accounted for, the J(B-11,B-11) coupling constants for various [B-2(CN)(6)](2-) salts were measured to range from 29.4 to 35.8 Hz, and their electronic origins were determined using natural localized molecular orbital and natural bond orbital analyses. The coupling constants were found to strongly correlate to the hybridization states of the boron orbitals that form the B-B bonds and to the strength of the B-B bonds. This study provides a novel tool to study dynamics in ordered and disordered solids and provides new perspectives on electron-precise dianionic diboranes featuring two-center-two-electron bonds in the context of related compounds featuring multiply and singly bonded boron spin pairs.