Organoamido- and Aryloxo-lanthanoids. XIII: Organometallic Compounds of the Lanthanoids. CV: New Lanthanoid(Ⅲ) Complexes with Pyrazolate Ligands

摘要

Die Komplexe Er(Me_2pz)_3(thf) und Ln(Ph_2pz)_3(thf)_n (Ln = Sc, Y, Cd, Er, n = 2; Ln = Lu, n = 3) (Me_2pz~- = 3,5-Dimethylpyrazolat, thf = Tetrahydrofuran, Ph_2pz~- = 3,5-Diphenylpyrazolat) wurden durch Reaktion der Lanthanoid-Metalle mit Bis(pentafluorophenyl)quecksilber und den entsprechenden Pyrazolderivaten in thf dargestellt. In den Komplexen Ln(Ph_2pz)_3(thf)_2 besetzen drei η~2-Ph_2pz Liganden sechs der acht Koordinationsstellen am Ln. Die Pyrazolat-komplexe, Y(pz)_3(thf)_2, La(Me_2pz)_3(thf), Cp_2Ln(Me_2pz)(thf)_n (Ln = Y, Lu, n = 0; Ln = Lu, n = 1), (C_5Me_5)_2Y(pz)(thf), (C_5Me_5)_2Y(Mepz)(thf), (C_5Me_5)_2Y(Me_2pz)(thf)_2 (pz~- = Pyrazolat, Mepz~- = 3-Methylpyrazolat, Cp = Cyclopentadienyl) wurden durch Reaktion von LnCl_3, Cp_2LnCl oder (C_5Me_5)_2LnCl mit den entsprechenden Natriumpyrazolaten in thf erhalten. Die Komplexe Ln(Me_2pz)_3(thf) (Ln = La, Er) sind symmetrische Dimere mit vier chelatisierenden und zwei verbrückenden Me_2pz Gruppen neben zwei verbrückenden thf Liganden. Die Cyclopentadienylkomplexe liegen als Dimere mit verbrückenden Pyrazolatgruppen und eingelagertem thf vor.%The complexes Er(Me_2pz)_3(thf) and Ln(Ph_2pz)_3(thf)_n (Ln = Sc, Y, Gd, Er, n = 2; Ln = Lu, n = 3) (Me_2pz~- = 3,5-dimethylpyrazolate, thf = tetrahydrofuran, Ph_2pz~- = 3,5-di-phenylpyrazolate) have been prepared by reaction of the lan-thanoid metal with bis(pentafluorophenyl)mercury and the pyrazole in thf. The Ln(Ph_2pz)_3(thf)_2 complexes are considered to be eight coordinate with three η ~2-Ph_2pz ligands. Other lan-thanoid pyrazolate complexes, Y(pz)_3(thf)_2, La(Me_2pz)_3(thf), Cp_2Ln(Me_2pz)(thf)_n (Ln = Y, Lu, n = 0; Ln = Lu, n = 1), (C_5Me_5)_2Y(pz)(thf), (C_5Me_5)_2Y(Mepz)(thf), (C_5Me_5)_2Y(Me_2pz)- (thf)_2 (pz~- = pyrazolate, Mepz~- = 3-methylpyrazolate, Cp = cyclopentadienyl) have been synthesized by reaction of LnCl_3, Cp_2LnCl, or (C_5Me_5)_2LnCl with the appropriate sodium pyrazolate in thf. The structure of Ln(Me_2pz)_3(thf) (Ln = La or Er) is considered to be a symmetrical dimer with four chelating and two bridging Me_2pz groups, and two bridging thf ligands, whereas the cyclopentadienyl complexes are most likely dimers with bridging pyrazolate groups, and lattice thf of solvation.