C–H Bond Activation by a Palladium(II) Thioether Complex: Formation of the Bis(nitromethanate) Complex [Pd(9S3)(CH₂NO₂)₂]

Palladium­(II) acetate reacts with 1 equiv of 1,4,7-trithiacyclononane (9S3) at room temperature to produce the neutral complex [Pd­(9S3)­(OAc)₂] (<b>1</b>; OAc^– = CH₃COO^–) as an analytically pure yellow solid, which has been characterized using ¹H and ¹³C NMR spectroscopy and single-crystal X-ray diffraction. The crystal structure of <b>1</b> shows the first example of an <i>exodentate</i> third sulfur of the 9S3 ligand in a Pd­(II) complex. Complex <b>1</b> reacts with nitromethane at room temperature in methanol to produce [Pd­(9S3)­(CH₂NO₂)₂] (<b>2</b>) and acetic acid, as confirmed by ¹H NMR and ¹³C NMR spectroscopy. Moreover, complex <b>2</b> has been characterized by single-crystal X-ray diffraction. Its crystal structure is the first example of any transition-metal complex containing <i>two</i> nitromethanate (anionic nitromethane) ligands. The complex shows the more typical elongated-square-pyramidal structure and [S₂C₂ + S₁] coordination with one long Pd–S axial interaction at 2.823(2) Å and two C-bound nitromethanate ligands. Interestingly, each nitromethanate ligand is in a different coordination environment and varies in their trans-directing abilities. Reactivity studies suggest that the complexation behavior of the 9S3 ligand and the Pd­(II) center as well as the σ-donor ability of the leaving group play key roles in the C–H activation of the nitromethane. Two related metal complexes, [Pd­(dppe)­(OAc)₂] (dppe = 1,2-bis­(diphenylphosphino)­ethane) and [Pd­(9S3)­(CF₃COO)₂], were synthesized, but neither of these react in a similar fashion to form a nitromethanate complex. Also, the reaction of <b>1</b> with nitrobenzene and nitrocyclopentane was studied, but these nitro-organics do not undergo C–H bond activation like nitromethane

Metal-Ion-Complexing Properties of 2-(Pyrid-2′-yl)-1,10-phenanthroline, a More Preorganized Analogue of Terpyridyl. A Crystallographic, Fluorescence, and Thermodynamic Study

Some metal-ion-complexing properties of the ligand 2-(pyrid-2′-yl)-1,10-phenanthroline (MPP) are reported. MPP is of interest in that it is a more preorganized version of 2,2′;6,2″-terpyridine (tpy). Protonation constants (p<i>K</i>₁ = 4.60; p<i>K</i>₂ = 3.35) for MPP were determined by monitoring the intense π–π* transitions of 2 × 10^–5 M solutions of the ligand as a function of the pH at an ionic strength of 0 and 25 °C. Formation constants (log <i>K</i>₁) at an ionic strength of 0 and 25 °C were obtained by monitoring the π–π* transitions of MPP titrated with solutions of the metal ion, or 1:1 solutions of MPP and the metal ion were titrated with acid. Large metal ions such as Ca^II or La^III showed increases of log <i>K</i>₁ of about 1.5 log units compared to that of tpy. Small metal ions such as Zn^II and Ni^II showed little increase in log <i>K</i>₁ for MPP compared to the tpy complexes, which is attributed to the presence of five-membered chelate rings in the MPP complexes, which favor large metal ions. The structure of [Cd­(MPP)­(H₂O)­(NO₃)₂] (<b>1</b>) is reported: monoclinic, <i>P</i>2₁/<i>c</i>, <i>a</i> = 7.4940(13) Å, <i>b</i> = 12.165(2) Å, <i>c</i> = 20.557(4) Å, β = 96.271(7)°, <i>V</i> = 1864.67(9) ų, <i>Z</i> = 4, and final <i>R</i> = 0.0786. The Cd in <b>1</b> is seven-coordinate, comprising the three donor atoms of MPP, a coordinated water, a monodentate, and a bidentate NO₃^–. Cd^II is a fairly large metal ion, with <i>r</i>⁺ = 0.96 Å, slightly too small for coordination with MPP. The effect of this size matching in terms of the structure is discussed. Fluorescence spectra of 2 × 10^–7 M MPP in aqueous solution are reported. The nonprotonated MPP ligand fluoresces only weakly, which is attributed to a photoinduced-electron-transfer effect. The chelation-enhanced-fluorescence (CHEF) effect induced by some metal ions is presented, and the trend of the CHEF effect, which is Ca^II > Zn^II > Cd^II ∼ La^III > Hg^II, is discussed in terms of factors that control the CHEF effect, such as the heavy-atom effect

Selectivity of the Highly Preorganized Tetradentate Ligand 2,9-Di(pyrid-2-yl)-1,10-phenanthroline for Metal Ions in Aqueous Solution, Including Lanthanide(III) Ions and the Uranyl(VI) Cation

Some metal ion complexing properties of DPP (2,9-Di­(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln­(III) (Lanthanide­(III)) ions and alkali earth metal ions, as well as the uranyl­(VI) cation. The intense π–π* transitions in the absorption spectra of aqueous solutions of 10^–5 M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln­(III) (Ln = lanthanide) ions. It was found that log <i>K</i>₁(DPP) for the Ln­(III) ions has a peak at Ln­(III) = Sm­(III) in a plot of log <i>K</i>₁ versus 1/<i>r</i>⁺ (<i>r</i>⁺ = ionic radius for 8-coordination). For Ln­(III) ions larger than Sm­(III), there is a steady rise in log <i>K</i>₁ from La­(III) to Sm­(III), while for Ln­(III) ions smaller than Sm­(III), log <i>K</i>₁ decreases slightly to the smallest Ln­(III) ion, Lu­(III). This pattern of variation of log <i>K</i>₁ with varying size of Ln­(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln­(DPP)­(H₂O)₅]³⁺ and [Ln­(qpy)­(H₂O)₅]³⁺ (qpy = quaterpyrdine) complexes of all the Ln­(III) ions. The ideal M–N bond lengths used for the Ln­(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln­(III) ions with polypyridyl ligands. Similarly, the ideal M–O bond lengths were those for complexes of the Ln­(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M–N length, a minimum in ∑U occurred at Pm­(III), adjacent in the series to Sm­(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am­(III) and Ln­(III) ions in the treatment of nuclear waste, and (2) Am­(III) is very close in M–N bond lengths to Pm­(III), so that an important aspect of the selectivity of polypyridyl type ligands for Am­(III) will depend on the above metal ion size-based selectivity. The selectivity patterns of DPP with the alkali-earth metal ions shows a similar preference for Ca­(II), which has the most appropriate M–N lengths. The structures of DPP complexes of Zn­(II) and Bi­(III), as representative of a small and of a large metal ion respectively, are reported. [Zn­(DPP)₂]­(ClO₄)₂ (triclinic, <i>P</i>1, <i>R</i> = 0.0507) has a six-coordinate Zn­(II), with each of the two DPP ligands having one noncoordinated pyridyl group appearing to be π-stacked on the central aromatic ring of the other DPP ligand. [Bi­(DPP)­(H₂O)₂(ClO₄)₂]­(ClO₄) (triclinic, <i>P</i>1, <i>R</i> = 0.0709) has an eight-coordinate Bi, with the coordination sphere composed of the four N donors of the DPP ligand, two coordinated water molecules, and the O donors of two unidentate perchlorates. As is usually the case with Bi­(III), there is a gap in the coordination sphere that appears to be the position of a lone pair of electrons on the other side of the Bi from the DPP ligand. The Bi-L bonds become relatively longer as one moves from the side of the Bi containg the DPP to the side where the lone pair is thought to be situated. A DFT analysis of [Ln­(tpy)­(H₂O)_<i>n</i>]³⁺ and [Ln­(DPP)­(H₂O)₅]³⁺ complexes is reported. The structures predicted by DFT are shown to match very well with the literature crystal structures for the [Ln­(tpy)­(H₂O)_<i>n</i>]³⁺ with Ln = La and <i>n</i> = 6, and Ln = Lu with <i>n</i> = 5. This then gives one confidence that the structures for the DPP complexes generated by DFT are accurate. The structures generated by DFT for the [Ln­(DPP)­(H₂O)₅]³⁺ complexes are shown to agree very well with those generated by MM, giving one confidence in the accuracy of the latter. An analysis of the DFT and MM structures shows the decreasing O--O nonbonded distances as one progresses from La to Lu, with these distances being much less than the sum of the van der Waals radii for the smaller Ln­(III) ions. The effect that such short O--O nonbonded distances has on thermodynamic complex stability and coordination number is then discussed