Abstract
| Language | English |
|---|---|
| Pages | 1481-1486 |
| Number of pages | 5 |
| Journal | Dalton Transactions |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 2008 |
Fingerprint
Keywords
- directed ortho-metalation
- inverse crown chemistry
- cross-coupling symbiosis
- aryl compounds
- crystal-structures
- molecular-structure
- alkyl
- complexes
- deprotonation
- phenylethynyl
Cite this
}
Synthesis and characterisation of new bimetallic alkali metal-magnesium mixed diisopropylamide-acetylides: structural variations in bimetallic lithium- and sodium-heteroleptic magnesiates. / Garcia-Alvarez, J.; Graham, D.V.; Hevia, E.; Kennedy, A.R.; Mulvey, R.E.
In: Dalton Transactions, No. 11, 2008, p. 1481-1486.Research output: Contribution to journal › Article
TY - JOUR
T1 - Synthesis and characterisation of new bimetallic alkali metal-magnesium mixed diisopropylamide-acetylides: structural variations in bimetallic lithium- and sodium-heteroleptic magnesiates
AU - Garcia-Alvarez, J.
AU - Graham, D.V.
AU - Hevia, E.
AU - Kennedy, A.R.
AU - Mulvey, R.E.
PY - 2008
Y1 - 2008
N2 - 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.
AB - 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.
KW - directed ortho-metalation
KW - inverse crown chemistry
KW - cross-coupling symbiosis
KW - aryl compounds
KW - crystal-structures
KW - molecular-structure
KW - alkyl
KW - complexes
KW - deprotonation
KW - phenylethynyl
UR - http://dx.doi.org/10.1039/b716215d
U2 - 10.1039/b716215d
DO - 10.1039/b716215d
M3 - Article
SP - 1481
EP - 1486
JO - Dalton Transactions
T2 - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 11
ER -