Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(μ-Cp^An)Y(μ-H)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂), with a 3.4 Å Yttrium-Yttrium Distance

The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d¹ Y(II) ions. The precursor [Cp^AnY(μ-H)(THF)]₂ (Cp^An = Me₂Si[C₅H₃(SiMe₃)-3]₂) was synthesized by hydrogenolysis of the allyl complex Cp^AnY(η³-C₃H₅)(THF), which was prepared from (C₃H₅)MgCl and [Cp^AnY(μ-Cl)]₂. Treatment of [Cp^AnY(μ-H)(THF)]₂ with excess KC₈ in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(μ-Cp^An)Y(μ-H)]₂. The two rings of each Cp^An ligand in the reduced anion [(μ-Cp^An)Y(μ-H)]₂^1- are attached to two yttrium centers in a “flyover” configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)₂][(μ-Cp^An)Dy(μ-H)]₂, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f⁹ Dy(III) center and one 4f⁹(5d_z)¹ Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.