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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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Received: 8 November 2013; in revised form: 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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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MDPI and ACS Style

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.

AMA Style

Marshall G, Wooles AJ, Mills DP, Lewis W, Blake AJ, Liddle ST. Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides. Inorganics. 2013; 1(1):46-69.

Chicago/Turabian Style

Marshall, George; Wooles, Ashley J.; Mills, David P.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. 2013. "Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides." Inorganics 1, no. 1: 46-69.

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