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Abstract
The reactivity of the Brønsted basic mixed-metal tris-amide compounds of empirical formula [MMg(NiPr2)3] [where M = Li ( 1), Na ( 2)] towards phenylacetylene (HCCPh) has been investigated and has led to the synthesis of a series of mixed-metal acetylido-amido-magnesiates. Thus, 1 and 2 molar equivalents of the alkyne with [MMg(NiPr2)3] produce heteroanionic bis(amido)-mono(acetylido) [LiMg(NiPr2)2(CCPh)]2 ( 3) and mono(amido)-bis(acetylido) [(TMEDA)·Na(CCPh)2Mg(NiPr2)]2 ( 4) (TMEDA = N,N,N,N-tetramethylethylenediamine) respectively. X-Ray crystallographic studies reveal that the new compounds adopt a different structural motif. Complex 3 can be defined as an inverse crown structure, having a cationic eight-atom [(NaNMgN)2]2+ ring which hosts in its core two acetylido ligands. On the other hand, 4 adopts a tetranuclear NaMgMgNa near-linear chain arrangement, held together by acetylido and amido bridges. The metal coordination geometries in both structures are distorted tetrahedral, and the sodium cations at the end of the mixed-metal chain carry terminal chelating TMEDA ligands. 1H and 13C NMR spectral data recorded in C6D6 solutions are also reported for 3 and 4, and are consistent with the solid-state structures being retained in solution.
Original language | English |
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Pages (from-to) | 1481-1486 |
Number of pages | 5 |
Journal | Dalton Transactions |
Issue number | 11 |
DOIs | |
Publication status | Published - 2008 |
Keywords
- directed ortho-metalation
- inverse crown chemistry
- cross-coupling symbiosis
- aryl compounds
- crystal-structures
- molecular-structure
- alkyl
- complexes
- deprotonation
- phenylethynyl
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