Synthesis, properties and crystal structures of 6-, 7- and 8-coordinate Zr(iv) and Hf(iv) complexes involving thioether and selenoether ligands

Shape and Symmetry of Heptacoordinate Transition‐Metal Complexes: Structural Trends

“…The experimental structures of complexes of the type [M(tacn)L 4 ] (data provided as Supporting Information) are found as CO [53] or CTP [54,55] structures, and complexes with the analogous sulfur macro- cycle [9]ane-S 3 also present CO coordination spheres. [56,57] The coordination sphere of one tacn complex [58] seems to be closer to the PBP geometry, but this has a side-bound peroxo ligand. If the peroxo ligand is considered to occupy one coordination position, octahedral coordination might be expected and the approximate PBP shape indicates that it is nearly coplanar with three other mer ligands.…”

Structural, Electrochemical, and Theoretical Investigations of New Thio‐ and Selenoether Complexes of Molybdenum and Tungsten

“…[11,12] High-valent metal complexes with thioether or selenoether ligands that represent hard-soft metal-ligand combinations are relatively rare mainly because these compounds are rather unstable. [13] Even though molybdenum(vi) and tungsten(vi) can be considered as moderately hard, only a handful of thioether or selenoether complexes of these metals are known. [14][15][16][17] In spite of the assumption that these kinds of complexes with Mo VI and W VI may not be easy to prepare and handle, we tried to synthesize and characterize a small variety of these compounds with additional alkoxy functions at the ligands for enhanced stability.…”

An Unexpected Photoelectronic Effect from [Co(en)3]2(Zr2F12)(SiF6)⋅4 H2O, a Compound Containing an H‐Bonded Assembly of Discrete [Co(en)3]3+, (Zr2F12)4−, and (SiF6)2− Ions

“…The UV/Vis absorption spectrum of 1 shows three bands with maxima at approximately 237, 337, and 465 nm (Fig- [14] whereas that at about 237 nm, which is absent in K 4 Zr 2 F 12 but is commonly found in many zirconium-containing compounds, [15] is tentatively assigned to a ligand-to-metal charge-transfer (LMCT) from the fluoride to the zirconium center. As K 4 Zr 2 F 12 itself does not absorb at wavelengths longer than 200 nm, the absorption at about 237 nm in 1 suggests that the HOMO-LUMO gap of [Zr 2 F 12 ] 4À in 1 may be smaller than that in K 4 Zr 2 F 12 .…”