%0 Journal Article
%T Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides
%A George Marshall
%A Ashley J. Wooles
%A David P. Mills
%A William Lewis
%A Alexander J. Blake
%A Stephen T. Liddle
%J Inorganics
%D 2013
%R 10.3390/inorganics1010046
%X We report the extension of the series of {BIPM TMSH} ˋ (BIPM R = C{PPh 2NR} 2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPM TMSH)(I) 2(THF)] (Ln = Nd, Gd, Tb), 1a每c, in 34每50% crystalline yields via the reaction of [Ln(I) 3(THF) 3.5] with [Cs(BIPM TMSH)]. Similarly, we have extended the range of {BIPM MesH} ˋ (Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPM MesH)(I) 2(THF) 2], 3, (49%) and [Yb(BIPM MesH)(I) 2(THF)], 4, (26%), via the reaction of [Ln(I) 3(THF) 3.5] with [{K(BIPM MesH)} 2]. Attempts to prepare dysprosium and erbium analogues of 3 or 4 were not successful, with the ion pair species [Ln(BIPM MesH) 2][BIPM MesH] (Ln ˋ= Dy, Er), 5a每b, isolated in 31每39% yield. The TMEDA ( N', N', N", N"-tetramethylethylenediamine) adducts [Ln(BIPM MesH)(I) 2(TMEDA)] (Ln = La, Gd), 6a每b, were prepared in quantitative yield via the dissolution of [La(BIPM MesH)(I) 2(THF)] or 3 in a TMEDA/THF solution. The reactions of [Ln(BIPM MesH)(I) 2(THF)] [Lnˋ = La, Ce, Pr, and Gd ( 3)] or 6a每b with a selection of bases did not afford [La(BIPM Mes)(I)(S) n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPM Mes)(BIPM MesH)] (Ln = La, Ce, Pr and Gd), 7a每 d, in low yields due to ligand scrambling.
%K lanthanide
%K methanide
%K methanediide
%U http://www.mdpi.com/2304-6740/1/1/46