Crystal structure of a heavier alkali metal diisopropylamide complex: a discrete (KN)(2) ring dimer with TMEDA chelation and short intramolecular K center dot center dot center dot H(C)contacts

W Clegg, S Kleditzsch, Robert Mulvey, P O'Shaughnessy

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Abstract

Synthesized by treating diisopropylamine with a potassium reagent (the solid isolated from a 1:1 reaction mixture of potassium t-butoxide and n-butyllithium) in the presence of N,N,N',N'-tetramethylenediamine (TMEDA), the potassium diisopropylamide complex [((Pr2NK)-Pr-i. TMEDA)(2)] has been subjected to a low temperature X-ray diffraction study. This reveals a discrete dimeric arrangement centred on an asymmetrical (KN)(2) cyclic ring, with bond lengths of 2.706(2) and 2.837(2) Angstrom and endocyclic bond angles of 100.54(5) and 79.46(5)degrees (at K and N, respectively). Terminal, chelating TMEDA ligands complete the distorted tetrahedral N, primary coordination sphere about the K+ cations. However, there are several secondary intramolecular K ... H(C) contacts involving methyl fragments of the diisopropylamido ligands. (C) 1998 Elsevier Science S.A. All rights reserved.

LanguageEnglish
Pages193-196
Number of pages4
JournalJournal of Organometallic Chemistry
Volume558
Issue number1-2
DOIs
Publication statusPublished - 15 May 1998

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Alkali Metals
chelation
Putrescine
Coordination Complexes
Alkali metals
heavy metals
Metal complexes
Heavy Metals
Chelation
Dimers
alkali metals
Heavy metals
Potassium
potassium
Crystal structure
dimers
crystal structure
rings
Ligands
ligands

Keywords

  • amide
  • crystal structure
  • intramolecular bonding
  • potassium
  • lithium
  • sodium
  • reactivity
  • amides
  • LDA

Cite this

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title = "Crystal structure of a heavier alkali metal diisopropylamide complex: a discrete (KN)(2) ring dimer with TMEDA chelation and short intramolecular K center dot center dot center dot H(C)contacts",
abstract = "Synthesized by treating diisopropylamine with a potassium reagent (the solid isolated from a 1:1 reaction mixture of potassium t-butoxide and n-butyllithium) in the presence of N,N,N',N'-tetramethylenediamine (TMEDA), the potassium diisopropylamide complex [((Pr2NK)-Pr-i. TMEDA)(2)] has been subjected to a low temperature X-ray diffraction study. This reveals a discrete dimeric arrangement centred on an asymmetrical (KN)(2) cyclic ring, with bond lengths of 2.706(2) and 2.837(2) Angstrom and endocyclic bond angles of 100.54(5) and 79.46(5)degrees (at K and N, respectively). Terminal, chelating TMEDA ligands complete the distorted tetrahedral N, primary coordination sphere about the K+ cations. However, there are several secondary intramolecular K ... H(C) contacts involving methyl fragments of the diisopropylamido ligands. (C) 1998 Elsevier Science S.A. All rights reserved.",
keywords = "amide, crystal structure, intramolecular bonding, potassium, lithium, sodium, reactivity, amides, LDA",
author = "W Clegg and S Kleditzsch and Robert Mulvey and P O'Shaughnessy",
year = "1998",
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T1 - Crystal structure of a heavier alkali metal diisopropylamide complex: a discrete (KN)(2) ring dimer with TMEDA chelation and short intramolecular K center dot center dot center dot H(C)contacts

AU - Clegg, W

AU - Kleditzsch, S

AU - Mulvey, Robert

AU - O'Shaughnessy, P

PY - 1998/5/15

Y1 - 1998/5/15

N2 - Synthesized by treating diisopropylamine with a potassium reagent (the solid isolated from a 1:1 reaction mixture of potassium t-butoxide and n-butyllithium) in the presence of N,N,N',N'-tetramethylenediamine (TMEDA), the potassium diisopropylamide complex [((Pr2NK)-Pr-i. TMEDA)(2)] has been subjected to a low temperature X-ray diffraction study. This reveals a discrete dimeric arrangement centred on an asymmetrical (KN)(2) cyclic ring, with bond lengths of 2.706(2) and 2.837(2) Angstrom and endocyclic bond angles of 100.54(5) and 79.46(5)degrees (at K and N, respectively). Terminal, chelating TMEDA ligands complete the distorted tetrahedral N, primary coordination sphere about the K+ cations. However, there are several secondary intramolecular K ... H(C) contacts involving methyl fragments of the diisopropylamido ligands. (C) 1998 Elsevier Science S.A. All rights reserved.

AB - Synthesized by treating diisopropylamine with a potassium reagent (the solid isolated from a 1:1 reaction mixture of potassium t-butoxide and n-butyllithium) in the presence of N,N,N',N'-tetramethylenediamine (TMEDA), the potassium diisopropylamide complex [((Pr2NK)-Pr-i. TMEDA)(2)] has been subjected to a low temperature X-ray diffraction study. This reveals a discrete dimeric arrangement centred on an asymmetrical (KN)(2) cyclic ring, with bond lengths of 2.706(2) and 2.837(2) Angstrom and endocyclic bond angles of 100.54(5) and 79.46(5)degrees (at K and N, respectively). Terminal, chelating TMEDA ligands complete the distorted tetrahedral N, primary coordination sphere about the K+ cations. However, there are several secondary intramolecular K ... H(C) contacts involving methyl fragments of the diisopropylamido ligands. (C) 1998 Elsevier Science S.A. All rights reserved.

KW - amide

KW - crystal structure

KW - intramolecular bonding

KW - potassium

KW - lithium

KW - sodium

KW - reactivity

KW - amides

KW - LDA

U2 - 10.1016/S0022-328X(98)00391-X

DO - 10.1016/S0022-328X(98)00391-X

M3 - Article

VL - 558

SP - 193

EP - 196

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

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ER -