Synthesis and structural characterization of the first lanthanide tris(phosphido) complex: Tm[P(SiMe3)2]3(thf)2

Abstract

TmI₃(thf)_x(x= 3.5) reacts with 3 equiv. of KP(SiMe₃)₂ in thf at room temperature to form an orange suspension from which trivalent Tm[P(SiMe₃)₂]₃(thf)₂, 1, can be isolated in 60% yield (monoclinic, space group C2/c, four molecules in the unit cell); the structure of 1 features the five-coordinate thulium atom in a distorted trigonal bipyramidal environment with two thf molecules in the axial and the bis(trimethylsilyl)phosphido ligands in the equatorial positions.