Tetraamine Me6TREN induced monomerization of alkali metal borohydrides and aluminohydrides

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Abstract

Monomeric 1:1 complexes of MEH4 (M, E = Li, B, 1; Na, B, 2; Li, Al, 3; Na, Al, 4) and the tripodal tetradentate ligand (Me2NCH2CH2)3N (Me6TREN) have been prepared in good yields by refluxing in THF and allowing the solutions to cool slowly. X-ray diffraction studies show that the BH4 group binds to either Li or Na via three hydride bridges while the AlH4 group connects to Li via a single hydride bridge. Surprisingly, Me6TREN·LiAlH4 represents the first monomeric contacted ion pair LiAlH4 derivative to be structurally characterized. In every case the tetraamine coordinates via all four of its Lewis basic nitrogen atoms. A similar protocol using the alkyl-rich borohydride MBEt3H also gives monomeric species (M = Li, 5; Na, 6). All complexes have been characterized in solution by multinuclear (1H, 7Li, 11B, 13C and 27Al, where appropriate) NMR spectroscopy which reveals excellent textbook examples of 1J coupling between B/Al and H in the cases of complexes 1-4 and between B and C in the cases of complexes 5 and 6.
LanguageEnglish
Pages94-99
Number of pages6
JournalPolyhedron
Volume103A
Early online date11 Sep 2015
DOIs
Publication statusPublished - 8 Jan 2016

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Alkali Metals
Borohydrides
borohydrides
Alkali metals
Hydrides
alkali metals
hydrides
textbooks
Textbooks
nitrogen atoms
Nuclear magnetic resonance spectroscopy
Nitrogen
Ligands
Ions
Derivatives
X ray diffraction
Atoms
nuclear magnetic resonance
ligands
diffraction

Keywords

  • NMR spectroscopy
  • tetraamine
  • alkali metal borohydrides

Cite this

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title = "Tetraamine Me6TREN induced monomerization of alkali metal borohydrides and aluminohydrides",
abstract = "Monomeric 1:1 complexes of MEH4 (M, E = Li, B, 1; Na, B, 2; Li, Al, 3; Na, Al, 4) and the tripodal tetradentate ligand (Me2NCH2CH2)3N (Me6TREN) have been prepared in good yields by refluxing in THF and allowing the solutions to cool slowly. X-ray diffraction studies show that the BH4 group binds to either Li or Na via three hydride bridges while the AlH4 group connects to Li via a single hydride bridge. Surprisingly, Me6TREN·LiAlH4 represents the first monomeric contacted ion pair LiAlH4 derivative to be structurally characterized. In every case the tetraamine coordinates via all four of its Lewis basic nitrogen atoms. A similar protocol using the alkyl-rich borohydride MBEt3H also gives monomeric species (M = Li, 5; Na, 6). All complexes have been characterized in solution by multinuclear (1H, 7Li, 11B, 13C and 27Al, where appropriate) NMR spectroscopy which reveals excellent textbook examples of 1J coupling between B/Al and H in the cases of complexes 1-4 and between B and C in the cases of complexes 5 and 6.",
keywords = "NMR spectroscopy, tetraamine, alkali metal borohydrides",
author = "Kennedy, {Alan R.} and Ross McLellan and McNeil, {Greg J.} and Mulvey, {Robert E.} and Robertson, {Stuart D.}",
year = "2016",
month = "1",
day = "8",
doi = "10.1016/j.poly.2015.08.046",
language = "English",
volume = "103A",
pages = "94--99",
journal = "Polyhedron",
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TY - JOUR

T1 - Tetraamine Me6TREN induced monomerization of alkali metal borohydrides and aluminohydrides

AU - Kennedy, Alan R.

AU - McLellan, Ross

AU - McNeil, Greg J.

AU - Mulvey, Robert E.

AU - Robertson, Stuart D.

PY - 2016/1/8

Y1 - 2016/1/8

N2 - Monomeric 1:1 complexes of MEH4 (M, E = Li, B, 1; Na, B, 2; Li, Al, 3; Na, Al, 4) and the tripodal tetradentate ligand (Me2NCH2CH2)3N (Me6TREN) have been prepared in good yields by refluxing in THF and allowing the solutions to cool slowly. X-ray diffraction studies show that the BH4 group binds to either Li or Na via three hydride bridges while the AlH4 group connects to Li via a single hydride bridge. Surprisingly, Me6TREN·LiAlH4 represents the first monomeric contacted ion pair LiAlH4 derivative to be structurally characterized. In every case the tetraamine coordinates via all four of its Lewis basic nitrogen atoms. A similar protocol using the alkyl-rich borohydride MBEt3H also gives monomeric species (M = Li, 5; Na, 6). All complexes have been characterized in solution by multinuclear (1H, 7Li, 11B, 13C and 27Al, where appropriate) NMR spectroscopy which reveals excellent textbook examples of 1J coupling between B/Al and H in the cases of complexes 1-4 and between B and C in the cases of complexes 5 and 6.

AB - Monomeric 1:1 complexes of MEH4 (M, E = Li, B, 1; Na, B, 2; Li, Al, 3; Na, Al, 4) and the tripodal tetradentate ligand (Me2NCH2CH2)3N (Me6TREN) have been prepared in good yields by refluxing in THF and allowing the solutions to cool slowly. X-ray diffraction studies show that the BH4 group binds to either Li or Na via three hydride bridges while the AlH4 group connects to Li via a single hydride bridge. Surprisingly, Me6TREN·LiAlH4 represents the first monomeric contacted ion pair LiAlH4 derivative to be structurally characterized. In every case the tetraamine coordinates via all four of its Lewis basic nitrogen atoms. A similar protocol using the alkyl-rich borohydride MBEt3H also gives monomeric species (M = Li, 5; Na, 6). All complexes have been characterized in solution by multinuclear (1H, 7Li, 11B, 13C and 27Al, where appropriate) NMR spectroscopy which reveals excellent textbook examples of 1J coupling between B/Al and H in the cases of complexes 1-4 and between B and C in the cases of complexes 5 and 6.

KW - NMR spectroscopy

KW - tetraamine

KW - alkali metal borohydrides

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U2 - 10.1016/j.poly.2015.08.046

DO - 10.1016/j.poly.2015.08.046

M3 - Article

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SP - 94

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