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Inorganics 2013, 1(1), 46-69; doi:10.3390/inorganics1010046
Article

Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides

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School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK
* Author to whom correspondence should be addressed.
Received: 8 November 2013 / Revised: 4 December 2013 / Accepted: 5 December 2013 / Published: 12 December 2013
(This article belongs to the Special Issue Innovative Inorganic Synthesis)
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Abstract

We report the extension of the series of {BIPMTMSH} (BIPMR = C{PPh2NR}2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPMTMSH)(I)2(THF)] (Ln = Nd, Gd, Tb), 1a–c, in 34–50% crystalline yields via the reaction of [Ln(I)3(THF)3.5] with [Cs(BIPMTMSH)]. Similarly, we have extended the range of {BIPMMesH}(Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPMMesH)(I)2(THF)2], 3, (49%) and [Yb(BIPMMesH)(I)2(THF)], 4, (26%), via the reaction of [Ln(I)3(THF)3.5] with [{K(BIPMMesH)}2]. Attempts to prepare dysprosium and erbium analogues of 3 or 4 were not successful, with the ion pair species [Ln(BIPMMesH)2][BIPMMesH] (Ln  = Dy, Er), 5a–b, isolated in 31–39% yield. The TMEDA (N',N',N",N"-tetramethylethylenediamine) adducts [Ln(BIPMMesH)(I)2(TMEDA)] (Ln = La, Gd), 6a–b, were prepared in quantitative yield via the dissolution of [La(BIPMMesH)(I)2(THF)] or 3 in a TMEDA/THF solution. The reactions of [Ln(BIPMMesH)(I)2(THF)] [Ln  = La, Ce, Pr, and Gd (3)] or 6a–b with a selection of bases did not afford [La(BIPMMes)(I)(S)n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPMMes)(BIPMMesH)] (Ln = La, Ce, Pr and Gd), 7ad, in low yields due to ligand scrambling.
Keywords: lanthanide; methanide; methanediide lanthanide; methanide; methanediide
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Marshall, G.; Wooles, A.J.; Mills, D.P.; Lewis, W.; Blake, A.J.; Liddle, S.T. Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides. Inorganics 2013, 1, 46-69.

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