Oxidation and coupling of β-diketiminate ligand in lanthanide complexes: Novel eight-nuclear lanthanide clusters with μ-, μ₃-Cl, and μ₄-O bridge

Abstract

Two novel eight-nuclear lanthanide oxide and chloride clusters Ln(8)(μ-η(2)-L(4))(2)(μ(3)-Cl)(4)(μ-Cl)(10)(μ(4)-O)(3)(THF)(8) (Ln = Er(3), Dy(4); L(4) = [OC{(Me)CN-2,6-(i)PrC(6)H(3)}(2)](2-)) have been synthesized by the reaction of β-diketiminate rare-earth metal chlorides with oxygen, providing a new oxidation and coupling reaction of the β-diketiminate ligand.

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…90 The precise mechanism for this transformation remains unclear, but contrary to the aforementioned examples, lanthanide redox events are unlikely here. 90 The precise mechanism for this transformation remains unclear, but contrary to the aforementioned examples, lanthanide redox events are unlikely here.…”

Trinuclear, octanuclear and decanuclear dysprosium(III) complexes: Synthesis, structural and magnetic studies

“…Three further octanuclear clusters have been reported with square anti-prismatic, two linked tetrahedral and ''tub'' metallic core arrangements [18][19][20]. Compound 2 thus joins the small family of known octanuclear dysprosium clusters.…”

Unprecedented Octanuclear DyIII Cluster Exhibiting Single-Molecule Magnet Behavior

“…To the best of our knowledge, only two other lanthanide-based compounds exhibit a similar type of arrangement, wherein the cubane cores are linked by two μ 3 -η 2 -ON – or μ- O , O ′-carboxylato groups, , rather than a μ 4 -O 2– ligand. Also notable is an octanuclear compound in which four lanthanide ions are seen to form tetrahedra, connected by central μ 4 -O 2– ligands, thus giving rise to a distinct molecular architecture . In compound 1 , however, the μ 4 -O 2– moiety connects the two halves of the molecule, and forms cubane-like structures rather than tetrahedra connected by a central μ 4 -O 2– atom.…”