The ligand versus solvent behavior of Ni(+)(C6H6)3,4 complexes was studied using density functional theory all-electron calculations. Dispersion corrections were included with the BPW91-D2 method using the 6-311++G(2d,2p) basis set. The ground state (GS) for Ni(+)(C6H6)3 has three benzene rings 3d-π bonded to the metal. A two-layer isomer with two moieties coordinated η(3)-η(2) with Ni(+), and the other one adsorbed by van der Waals interactions to the Ni(+)(C6H6)2 subcluster, i.e., a 2 + 1 structure, is within about 8.4 kJ/mol of the GS. Structures with 3 + 1 and 2 + 2 ligand coordination were found for Ni(+)(C6H6)4. The binding energies (D0) of 28.9 and 26.0 kJ/mol for the external moieties of Ni(+)(C6H6)3,4 are much smaller than that for Ni(+)(C6H6)2, 193.0 kJ/mol, obtained also with BPW91-D2. This last D0 overestimates somehow the experimental value, of 146.7 ± 11.6 kJ/mol, for Ni(+)(C6H6)2. The abrupt fall for D0(Ni(+)(C6H6)3,4) shows that such molecules are bound externally as solvent species. These results agree with the D0(Ni(+)(C6H6)3) < 37.1 kJ/mol limit found experimentally for this kind of two-layer clusters. The ionization energies also decrease for m = 2, 3, and 4 (580.8, 573.1, and 558.6 kJ/mol). For Ni(+)(C6H6)3,4, each solvent moiety bridges the benzenes of Ni(+)(C6H6)2; their position and that of one internal ring mimics the tilted T-shape geometry of the benzene dimer (Bz2). The distances from the center of the external to the center of the internal rings for m = 3 (4.686 Å) and m = 4 (4.523 Å) are shorter than that for Bz2 (4.850 Å). This and charge transfer effects promote the (C(δ-)-H(δ+))(int) dipole-π(ext) interactions in Ni(+)(C6H6)3,4; π-π interactions also occur. The predicted IR spectra, having multiplet structure in the C-H region, provide insight into the experimental spectra of these ions.

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