Issue 38, 2014

Syntheses, structures and flexible coordination of sterically demanding di- and “tri”-lithiated methandiides

Abstract

Lithiation of the sterically demanding bis(iminophosphoranyl)methane H2C{Ph2P([double bond, length as m-dash]NDip)}2 (Dip = 2,6-iPr2C6H3), H2L, with alkyllithium reagents afforded the methandiide complexes [(LLi2)2] 2, [LLi2(OEt2)2] 4, [LLi2(THF)3] 5, [LLi2(THF)2] 6, and [LLi2(PMDTA)] 7 (PMDTA = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine), from various solvents or after the addition of donor molecules. The complex [HC(Ph2PNDip)(Ph2P)Li(THF)2] 3 was further identified as a by-product under certain conditions. Further lithiation of the methandiide in ortho-position of one P-bound phenyl group affords complexes of the trianionic ligand L′3−, and the complexes [(L′Li3)2] 8 and [L′Li3(THF)4] 9 were obtained. Different isomeric forms for the methandiide units investigated in solution and in the solid state are described, and the crystal structures of complexes 2, 3, and 5–9 are reported.

Graphical abstract: Syntheses, structures and flexible coordination of sterically demanding di- and “tri”-lithiated methandiides

Supplementary files

Article information

Article type
Paper
Submitted
23 Apr 2014
Accepted
27 May 2014
First published
27 May 2014

Dalton Trans., 2014,43, 14334-14345

Author version available

Syntheses, structures and flexible coordination of sterically demanding di- and “tri”-lithiated methandiides

C. P. Sindlinger and A. Stasch, Dalton Trans., 2014, 43, 14334 DOI: 10.1039/C4DT01185F

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