Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)3}2(μ-SPh)3][SPh] and Ln(SPh)3(hmpa)3(Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

Publisher Website
Google Scholar
Abstract
A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(μ-SAr)(thf)3]2 (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)2(py)4 (3, py = pyridine), and [{Ln(hmpa)3}2(μ-SPh)3][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)3(py)n(thf)3-n (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)3(hmpa)3 (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P212121 with a = 21.057(9), b = 25.963(7), c = 16.442(8) Å, V = 8988(5) Å3, Z = 4, R = 0.040, Rw = 0.039 for 5848 reflections with I > 3σ(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P1̄ with a = 14.719(3), b = 17.989(2), c = 11.344(2) Å, α = 97.91(1), β = 110.30(2), γ = 78.40(1)°, V = 2751.9(9) Å3, Z = 2, R = 0.045, Rw = 0.041 for 7111 reflections with I > 3σ(I) and 536 parameters; 13, triclinic, space group P1̄ with a = 14.565(2), b = 17.961(2), c = 11.302(1) Å, α = 97.72(1), β = 110.49(1), γ = 78.37(1)°, V = 2706.0(7) Å3, Z = 2, R = 0.031, Rw = 0.035 for 9837 reflections with I > 3σ(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln−S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.

This publication has 42 references indexed in Scilit: