Abstract
The study of quadruple bonds between transition metals, in particular those of dimolybdenum, has revealed much about the two-electron bond. The solid-state structure of the quadruple-bonded dimolybdenum(II) complex tetra-kis-[μ-4-(tri-fluoro-methyl)-benzoato-κ2 O:O']bis[(tetra-hydro-furan-κO)molybdenum(II)] 0.762-pentane 0.238-tetra-hydro-furan solvate, [Mo2(p-O2CC6H4CF3)4·2THF]·0.762C5H12·0.238C4H8O or [Mo2(C8H4F3O2)4(C4H8O)2]·0.762C5H12·0.238C4H8O is reported. The complex crystallizes within a triclinic cell and low symmetry (P ) results from the inter-calated penta-ne/THF solvent mol-ecules. The paddlewheel structure at 100 K has inversion symmetry and comprises four bridging carboxyl-ate ligands encases the Mo2(II,II) core that is characterized by two axially coordinated THF mol-ecules and an Mo-Mo distance of 2.1098 (7) Å.
Highlights
The 242 quadruple bond has contributed prominently to the elucidation of the single most distinguishing feature of the discipline of chemistry – the two-electron bond (Lewis, 1916)
To add further to an understanding of Mo2(II,II) quadruple bond distances, we examined a dimolybdenum core ligated by trifluoromethylbenzoate with THF axial donor ligands
We report the synthesis and X-ray crystal structure of tetrakis(-4-trifluoromethylbenzoato2O:O0)dimolybdenum(II) 0.762-pentane 0.238-tetrahydrofuran solvate [Mo2(p-O2CC6H4CF3)4Á2THF]Á0.762C5H12Á0.238C4H8O
Summary
The 242 quadruple bond has contributed prominently to the elucidation of the single most distinguishing feature of the discipline of chemistry – the two-electron bond (Lewis, 1916). Many subsequent structures have shown that the inductive effect of the R group on the carboxylic acid does not perturb the Mo—Mo bond distance, indicating the robustness of the two-electron bond within a quadruple-bond architecture. As proposed by Cotton (Cotton et al, 1978), the presence of ligands about the dimolybdenum center that are electron withdrawing and donating in the axial position is needed to perturb the overall bonding within a quadruple-bond framework. To this point, the metrics of [Mo2(p-O2CC6H4CF3)4ÁTHF] are indistinguishable from those of Mo2(O2CC6F5)4ÁTHF (Han, 2011). A donor ligand is needed in addition to electron-withdrawing carboxylate equatorial ligands to observe a difference in the dimolybdenum quadruple bond
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