Laser-ablated U atoms react with (CN)(2) in excess argon and neon during codeposition at 4 K to form UNC, U(NC)(2), and U(NC)(4) as the major uranium-bearing products, which are identified from their matrix infrared spectra using cyanogen substituted with C-13 and N-15 and from quantum chemical calculations. The (CN)-C-12/13 and (CN)-N-14/15 isotopic frequency ratios computed for the U(NC)(1,2,4) molecules agree better with the observed values than those calculated for the U(CN)(1,2,4) isomers. Multiplets using mixed isotopic cyanogens reveal the stoichiometries of these products, and the band positions and quantum chemical calculations confirm the isocyanide bonding minor major arrangements, which are 14 and 51 kJ/mol more stable than the cyanide isomers for UNC and U(NC)(2), respectively, and 62 kJ/mol for U(NC)(4) in the isolated gas phase at the CCSD(T)/CBS level. The studies further demonstrate that the isocyano nitrogen is a better pi donor, so it interacts with U(VI) better than carbon. Although the higher isocyanides are more stable than the corresponding cyanides, U(NC)(5) and U(NC)(6) were not observed here most likely because unfavorable or endothermic routes are required for their production from U(NC)(4). The computed U-NC bond dissociation energies decrease from 581 kJ/mol for 4[UNC] to 168 kJ/mol for 1[U(NC)(6)]. The ionic nature of U(NC) decreases as the number of isocyano groups increases.