Synthesis and Structural Characterization of Constrained-Geometry Organolanthanide Chlorides and Alkyls Incorporating the Ligand [η5:σ-(C9H6)C2B10H10]2−

Abstract

Interaction of 1-indenyl-1,2-carborane (1) with 2 equiv of KH in refluxing THF gave the dipotassium salt [K2][(C9H6)C2B10H10]. Treatment of [K2][(C9H6)C2B10H10] with 1 equiv of LnCl3 in THF generated the ionic complex [K(THF)6][{η5:σ-(C9H6)C2B10H10}2La(THF)] (2) for early lanthanide or organolanthanide chloride complexes [{η5:σ-(C9H6)C2B10H10}Ln(THF)2(μ-Cl)2K(THF)2]2 (Ln = Y (3a), Gd (3b), Er (3c), Yb (3d)) for late lanthanides. Reaction of 3 with nucleophile NaCp or KCH2C6H4-o-NMe2 afforded the corresponding salt metathesis products [η5:σ-(C9H6)C2B10H10]Ln(η5-C5H5)(THF)2 (Ln = Y (4a), Gd (4b)) or [η5:σ-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(DME) (Ln = Y (5a), Er (5c)), respectively. Complexes 5 were also synthesized via the alkane elimination reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)3. They represent the first examples of organolanthanide alkyl complexes incorporating a carboranyl ligand. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. Som...