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The effects of different terphenyl ligand substituents on the quintuple Cr−Cr bonding in arylchromium(I) dimers stabilized by bulky terphenyl ligands (Ar) were investigated. A series of complexes, ArCrCrAr (1−4; Ar = C₆H₂-2,6-(C₆H₃-2,6-ⁱPr₂)₂-4-X, where X = H, SiMe₃, OMe, and F), was synthesized and structurally characterized. Their X-ray crystal structures display similar trans-bent C(ipso)CrCrC(ipso) cores with short Cr−Cr distances that range from 1.8077(7) to 1.8351(4) Å. There also weaker Cr−C interactions [2.294(1)−2.322(2) Å] involving an C(ipso) of one of the flanking aryl rings. The data show that the changes induced in the Cr−Cr bond length by the different substituents X in the para positions of the central aryl ring of the terphenyl ligand are probably a result of packing rather than electronic effects. This is in agreement with density functional theory (DFT) calculations, which predict that the model …