U-CN versus Ce-NC coordination in trivalent complexes derived from M[N(SiMe3)2]3 (M = Ce, U). Reactions of [MN*3] (M = Ce, U; N* = N(SiMe3)2) and NR4CN (R = Me, Et, or (n)Bu) or KCN in the presence of 18-crown-6 afforded the series of cyanido-bridged dinuclear compounds [NEt4][(MN*3)2(μ-CN)] (M = Ce, 2a, and U, 2b), [K(18-crown-6)(THF)2][(CeN*3)2(μ-CN)] (2'a), and [K(18-crown-6)][(UN*3)2(μ-CN)] (2'b), and the mononuclear mono-, bis-, and tris(cyanide) complexes [NEt4][MN*3(CN)] (M = Ce, 1a(Et), and U, 1b(Et)), [NMe4][MN*3(CN)] (M = Ce, 1a(Me), and U, 1b(Me)), [K(18-crown-6)][MN*3(CN)] (M = Ce, 1'a, and U, 1'b), [N(n)Bu4]2[MN*3(CN)2] (M = Ce, 3a, and U, 3b), [K(18-crown-6)]2[MN*3(CN)2] (M = Ce, 3'a, and U, 3'b), and [N(n)Bu4]2[MN*2(CN)3] (M = Ce, 4a, and U, 4b).  The mono- and bis(cyanide) complexes were found to be in equilibrium.  The formation constant of 3'b (K3'b) from 1'b at 10 °C in THF is equal to 5(1) × 10(-3), and -ΔH3'b = 104(2) kJ mol(-1) and -ΔS3'b = 330(5) J mol(-1) K(-1).  The bis(cyanide) compound 3a or 3b was slowly transformed in solution into an equimolar mixture of the mono- and tris(cyanide) derivatives with elimination of N(n)Bu4N*.  The crystal structures of 1a(Me), 1b(Me), 1'a·toluene, 1'b·toluene, 2'a, 2'b, 3a, 3'a, 3'b, 3'a·2benzene, 3'b·2benzene, 4a·0.5THF, and 4b·Et2O were determined.  Crystals of the bis(cyanide) uranium complexes 3'b and 3'b·2benzene are isomorphous with those of the cerium counterparts 3'a and 3'a·2benzene, but they are not isostructural since the data revealed distinct coordination modes of the CN group, through the C or N atom to the U or Ce metal center, respectively.  This differentiation has been analyzed using density functional theory calculations.  The observed preferential coordination of the cyanide and isocyanide ions toward uranium or cerium in the bis(cyanide) complexes is corroborated by the consideration of the binding energies of these groups to the metals and by the comparison of DFT optimized geometries with the crystal structures.  The better affinity of the cyanide ligand toward U(III) over Ce(III) metal center is related to the better energy matching between the 6d/5f uranium orbitals and the cyanide ligand ones, leading to a non-negligible covalent character of the bonding.
C