Synthesis and structural characterisation of 'solvent-free' lithium-calcium hexamethyldisilazide, [Li{mu-N(SiMe3)(2)}(2)Ca{N(SiMe3)(2)}], exhibiting a double ration of agostic H3C center dot center dot center dot Li and H3C center dot center dot center dot Ca intramolecular interactions

A.R. Kennedy, R.E. Mulvey, R.B. Rowlings

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Abstract

Addition of lithium hexamethyldisilazide to an equimolar amount of calcium bis(hexamethyldisilazide) in toluene gave 'solvent-free'. [Li{mu-N(SiMc(3))(2)}(2)Ca{N(SiMe3)(2)] (1). An X-ray study reveals a dinuclear arrangement based on a planar LiNCaN four-membered ring: both metals engage in additional H3C...M (where M = Lt. Ca) interactions with the mu-N(SiMe3)(2) substituents resulting in a distorted tetrahedral geometry at lithium and a distorted trigonal-bipyramidal geometry at calcium. This contrasts with the previously reported mixed Li-Mg analogue, [Li{mu-N(SiMe3)(2)}(2)Mg{N(SiMe3)(2)}], where only the lithium centre engages in such intramolecular agostic H3C...Li interactions.
LanguageEnglish
Pages288-292
Number of pages4
JournalJournal of Organometallic Chemistry
Volume648
Issue number1-2
DOIs
Publication statusPublished - 2 Apr 2002

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rations
Lithium
calcium
Calcium
lithium
Geometry
Toluene
synthesis
Metals
X-Rays
interactions
geometry
X rays
toluene
analogs
rings
metals
lithium hexamethyldisilazide
x rays

Keywords

  • agostic
  • amide calcium
  • heterometallic
  • intramolecular interactions

Cite this

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title = "Synthesis and structural characterisation of 'solvent-free' lithium-calcium hexamethyldisilazide, [Li{mu-N(SiMe3)(2)}(2)Ca{N(SiMe3)(2)}], exhibiting a double ration of agostic H3C center dot center dot center dot Li and H3C center dot center dot center dot Ca intramolecular interactions",
abstract = "Addition of lithium hexamethyldisilazide to an equimolar amount of calcium bis(hexamethyldisilazide) in toluene gave 'solvent-free'. [Li{mu-N(SiMc(3))(2)}(2)Ca{N(SiMe3)(2)] (1). An X-ray study reveals a dinuclear arrangement based on a planar LiNCaN four-membered ring: both metals engage in additional H3C...M (where M = Lt. Ca) interactions with the mu-N(SiMe3)(2) substituents resulting in a distorted tetrahedral geometry at lithium and a distorted trigonal-bipyramidal geometry at calcium. This contrasts with the previously reported mixed Li-Mg analogue, [Li{mu-N(SiMe3)(2)}(2)Mg{N(SiMe3)(2)}], where only the lithium centre engages in such intramolecular agostic H3C...Li interactions.",
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AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - Rowlings, R.B.

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N2 - Addition of lithium hexamethyldisilazide to an equimolar amount of calcium bis(hexamethyldisilazide) in toluene gave 'solvent-free'. [Li{mu-N(SiMc(3))(2)}(2)Ca{N(SiMe3)(2)] (1). An X-ray study reveals a dinuclear arrangement based on a planar LiNCaN four-membered ring: both metals engage in additional H3C...M (where M = Lt. Ca) interactions with the mu-N(SiMe3)(2) substituents resulting in a distorted tetrahedral geometry at lithium and a distorted trigonal-bipyramidal geometry at calcium. This contrasts with the previously reported mixed Li-Mg analogue, [Li{mu-N(SiMe3)(2)}(2)Mg{N(SiMe3)(2)}], where only the lithium centre engages in such intramolecular agostic H3C...Li interactions.

AB - Addition of lithium hexamethyldisilazide to an equimolar amount of calcium bis(hexamethyldisilazide) in toluene gave 'solvent-free'. [Li{mu-N(SiMc(3))(2)}(2)Ca{N(SiMe3)(2)] (1). An X-ray study reveals a dinuclear arrangement based on a planar LiNCaN four-membered ring: both metals engage in additional H3C...M (where M = Lt. Ca) interactions with the mu-N(SiMe3)(2) substituents resulting in a distorted tetrahedral geometry at lithium and a distorted trigonal-bipyramidal geometry at calcium. This contrasts with the previously reported mixed Li-Mg analogue, [Li{mu-N(SiMe3)(2)}(2)Mg{N(SiMe3)(2)}], where only the lithium centre engages in such intramolecular agostic H3C...Li interactions.

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