Studies on organolanthanide complexes: LXIII. Synthesis, spectroscopic and X-ray crystallographic characterization of new early organolanthanide, organoyttrium hydride and organoholmium hydroxide complexes☆

Abstract Organolanthanide chloride complexes [(CH 3 OCH 2 CH 2 C 5 H 4 ) 2 Ln(μ-Cl)] 2 (Ln = La, Pr, Ho and Y) react with excess NaH in THF at 45°C to give the dimeric hydride complexes [(CH 3 OCH 2 CH 2 C 5 H 4 ) 2 Ln(μ-H)] 2 , which have been characterized by IR, 1 H NMR, MS and XPS spectroscopy, elemental analyses and X-ray crystallography. [(CH 3 OCH 2 CH 2 C 5 H 4 ) 2 Y(μ-H)] 2 crystallizes from THF/n-hexane at −30°C, in the triclinic space group P1 with a = 8.795(2) A, b = 11.040(1) A, c = 16.602(2) A, α = 93.73(1)°, β = 91.82(1)°, γ = 94.21(1)°, D c = 1.393 gcm −3 for Z = 2 dimers. However, crystals of [(CH 3 OCH 2 CH 2 C 5 H 4 ) 2 Ho(μ-OH)] 2 were obtained by recrystallization of holmium hydride in THF/n-hexane at −30°C, in the orthorhombic space group Pbca with a = 11.217(2) A, b = 15.865(7) A, c = 17.608(4) A, D c = 1.816 gcm −3 for Z = 4 dimers. In the complexes of yttrium and holmium, each Ln atom of the dimers is coordinated by two substituted cyclopentadienyl ligands, one oxygen atom and two hydrogen atoms (for the Y atom) or two hydroxyl groups (for the Ho atom) to form a distorted trigonal bipyramid if the C(η 5 )-bonded cyclopentadienyl is regarded as occupying a single polyhedral vertex.