Exploiting sigma/pi coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets

Matthew G. Davidson, Daniel Garcia-Vivo, Alan R. Kennedy, Robert E. Mulvey, Stuart D. Robertson

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Abstract

Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M center dot Me6TREN (M = Li, Na, K). The Li derivative displays a Li-C sigma interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of eta(4) coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized pi electrons whilst maintaining a partial sigma interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized pi system resulting in a planar CH2 group.

LanguageEnglish
Pages3364-3369
Number of pages6
JournalChemistry - A European Journal
Volume17
Issue number12
Early online date21 Feb 2011
DOIs
Publication statusPublished - 14 Mar 2011

Fingerprint

monomers
Monomers
Positive ions
Metals
Ligands
Derivatives
saturation
cations
ligands
Cations
pi-electrons
Scaffolds
metals
Potassium
potassium
Lithium
slip
Negative ions
lithium
Sodium

Keywords

  • alkali metals
  • benzyl anion
  • coordination isomerism
  • monomer
  • polyamines
  • X-RAY
  • crystal structure
  • benzyl complexes
  • organometallic compounds
  • potassium
  • lithium
  • sodium
  • reagents

Cite this

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title = "Exploiting sigma/pi coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets",
abstract = "Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M center dot Me6TREN (M = Li, Na, K). The Li derivative displays a Li-C sigma interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of eta(4) coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized pi electrons whilst maintaining a partial sigma interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized pi system resulting in a planar CH2 group.",
keywords = "alkali metals, benzyl anion, coordination isomerism, monomer, polyamines, X-RAY, crystal structure, benzyl complexes, organometallic compounds, potassium, lithium, sodium, reagents",
author = "Davidson, {Matthew G.} and Daniel Garcia-Vivo and Kennedy, {Alan R.} and Mulvey, {Robert E.} and Robertson, {Stuart D.}",
year = "2011",
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TY - JOUR

T1 - Exploiting sigma/pi coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets

AU - Davidson, Matthew G.

AU - Garcia-Vivo, Daniel

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - Robertson, Stuart D.

PY - 2011/3/14

Y1 - 2011/3/14

N2 - Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M center dot Me6TREN (M = Li, Na, K). The Li derivative displays a Li-C sigma interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of eta(4) coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized pi electrons whilst maintaining a partial sigma interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized pi system resulting in a planar CH2 group.

AB - Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M center dot Me6TREN (M = Li, Na, K). The Li derivative displays a Li-C sigma interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of eta(4) coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized pi electrons whilst maintaining a partial sigma interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized pi system resulting in a planar CH2 group.

KW - alkali metals

KW - benzyl anion

KW - coordination isomerism

KW - monomer

KW - polyamines

KW - X-RAY

KW - crystal structure

KW - benzyl complexes

KW - organometallic compounds

KW - potassium

KW - lithium

KW - sodium

KW - reagents

UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3765

U2 - 10.1002/chem.201003493

DO - 10.1002/chem.201003493

M3 - Article

VL - 17

SP - 3364

EP - 3369

JO - Chemistry - A European Journal

T2 - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 12

ER -