Unusual Two-Dimensional Sheet Structure of the Solvent-Free Cesium Aryloxide Complex CsO-2,6-i-Pr₂C₆H₃

Synthesis and characterization of lanthanide complexes bearing a ferrocene-containing N-aryloxo-β-ketoiminate ligand

“…[22]. The average bridging LaeO(Ar) bond length is, as expected, somewhat larger at 2.546(5) Å, which is also apparently larger than the bridging LaeO(Ar) bond length in (THF)La(Oe2,6e Pr i 2 C 6 H 3 ) 2 (meOe2,6ePr i 2 C 6 H 3 ) 2 M(THF) 2 (M ¼ Li, Na; 2.453(4) Å) [23], and the bridging LneO(Ar) bond length in complexes 1, 2, and 4 even when the difference in ionic radii is considered, indicating the increase of steric congestion around the lanthanum metal. The Li1eO2 and Li2AeO2 bond lengths are 1.94(2) and 1.92(1) Å, respectively, which indicated that the phenolate group is nearly symmetrically coordinated to two lithium atoms.…”

Synthesis of Group 1 Metal 2,6-Diphenylphenoxide Complexes [M(OC6H3Ph2-2,6)] (M = Li, Na, K, Rb, Cs) and Structures of the Solvent-Free Complexes [Rb(OC6H3Ph2-2,6)]x and [Cs(OC6H3Ph2-2,6)]x: One-Dimensional Extended Arrays of Metal Aryloxides

“…The rubidium and cesium complexes [Rb(OC 6 H 3 Ph 2 -2,6)] x ( 4 ) and [Cs(OC 6 H 3 Ph 2 -2,6)] x ( 5 ) were obtained via reaction of the pure metal with a benzene solution of the phenol. Neither 4 nor 5 has been previously reported in the literature, although the solvent-free cesium aryloxide complex [Cs(OC 6 H 3 Pr i 2 -2,6)] x ( 6 ) is known and has been structurally characterized; it has also been used for the preparation of [Cs 2 (La{OC 6 H 3 Pr 2 i -2,6} 5 ] . In the syntheses of 4 and 5 , an excess of the phenol was again employed, resulting in complete consumption of the alkali metal after stirring for 18 h. Evolution of dihydrogen was also observed in these reactions, although at a much slower rate than for the syntheses of 2 and 3 .…”

“…Substantially fewer potassium-containing derivatives are known, ,,,,− while even fewer rubidium and cesium aryloxide complexes have been structurally characterized. Examples of these include the picrate complexes [Rb(μ 2 -OC 6 H 2 (NO 2 ) 3 -2,4,6)] x and [Cs(μ 2 -OC 6 H 2 (NO 2 ) 3 -2,4,6)] x , , the racemic binaphthoxide solvates [Rb(OC 10 H 6 -C 10 H 6 OH)]·(HOC 10 H 6 C 10 H 6 OH) and Cs[OC 10 H 6 C 10 H 6 OH]· (HOC 10 H 6 C 10 H 6 OH), and the phenoxide complex [ Cs(OC 6 H 3 i Pr 2 -2,6)] x . The picrate and phenoxide complexes adopt polymeric structures in the solid state.…”

Trivalent lanthanide–alkene complexes: Crystallographic and NMR evidence for coordination of tethered alkenes in the solid state and solution

“…are interesting in this regard because the saturated isopropyl group is similar to an allyl group yet in this case, the distance from the lanthanide ion to all three isopropyl carbons lies well outside the sum of the van der Waals radii (Ln/C distance > 3.65 Å in all cases and usually >4 Å) [33,34]. Interestingly, these ate complexes do feature p-interactions but these are between the arene rings and the alkali metal cations not the lanthanide ions.…”