cis-2,6-Dimethylpiperidide: a structural mimic for TMP (2,2,6,6-tetramethypiperidide) or DA (diisopropylamide)?

R. Campbell, B. Conway, P. Garcia-Alvarez, A.R. Kennedy, J. Klett, C.T. O'Hara, R.E. Mulvey, G. Robertson, EPSRC (Funder)

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Four novel heterobimetallic ate complexes containing cis-2,6-dimethylpiperidide (cis-DMP) have been prepared and characterised. Two contain one cis-DMP ligand, namely the bisalkyl-amido lithium, and sodium zincates [(TMEDA)·MZn(cis-DMP)(tBu)2] (M = Li for 1, Na for 2). Both 1 and 2 are synthesised by co-complexation of the respective alkali metal amide with di-tert-butylzinc in the presence of a molar equivalent of N,N,N′,N′-tetramethylethylenediamine (TMEDA) in a hydrocarbon medium. The third complex, containing two cis-DMP ligands, is the alkyl-bisamido sodium zincate [(TMEDA)·NaZn(cis-DMP)2(tBu)] 3. Complex 3 is prepared from 2via a disproportionation reaction where the by-product is [(TMEDA)·NaZn(tBu)3]. Another alkyl-diamido sodium zincate, [(TMEDA)·NaZn(DIBA)2(tBu)] 4 is synthesised by utilising diisobutylamine [DIBA(H)]. This reaction emphasises the generality of this disproportionation process. Complex 5 contains three cis-DMP ligands and is a tris-amido sodium magnesiate [(TMEDA)·NaMg(cis-DMP)3]. It is prepared by treating an equimolar mixture of butylsodium and dibutylmagnesium with three and one molar equivalents of cis-DMP(H) and TMEDA respectively, in hydrocarbon solution. By comparison of 1-5 with appropriate complexes from the literature, it has been possible to experimentally determine that the steric bulk of cis-DMP closely resembles that of DA but is considerably less bulky than 2,2,6,6-tetramethylpiperidide (TMP).
LanguageEnglish
Pages511-519
Number of pages8
JournalDalton Transactions
Volume39
DOIs
Publication statusPublished - 2010

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Sodium
Hydrocarbons
Ligands
Alkali Metals
neurotensin mimic 2
cis-2,6-dimethylpiperidide
N,N,N',N'-tetramethylethylenediamine
Complexation
Lithium
Amides
Byproducts
5-((4-(4-(diethylamino)butyl)-1-piperidinyl)acetyl)-10,11-dihydrobenzo(b,e)(1,4)diazepine-11-one

Keywords

  • heterobimetallic ate complexes
  • cis-DMP
  • diisopropylamide

Cite this

Campbell, R. ; Conway, B. ; Garcia-Alvarez, P. ; Kennedy, A.R. ; Klett, J. ; O'Hara, C.T. ; Mulvey, R.E. ; Robertson, G. ; EPSRC (Funder). / cis-2,6-Dimethylpiperidide: a structural mimic for TMP (2,2,6,6-tetramethypiperidide) or DA (diisopropylamide)?. In: Dalton Transactions. 2010 ; Vol. 39. pp. 511-519.
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abstract = "Four novel heterobimetallic ate complexes containing cis-2,6-dimethylpiperidide (cis-DMP) have been prepared and characterised. Two contain one cis-DMP ligand, namely the bisalkyl-amido lithium, and sodium zincates [(TMEDA)·MZn(cis-DMP)(tBu)2] (M = Li for 1, Na for 2). Both 1 and 2 are synthesised by co-complexation of the respective alkali metal amide with di-tert-butylzinc in the presence of a molar equivalent of N,N,N′,N′-tetramethylethylenediamine (TMEDA) in a hydrocarbon medium. The third complex, containing two cis-DMP ligands, is the alkyl-bisamido sodium zincate [(TMEDA)·NaZn(cis-DMP)2(tBu)] 3. Complex 3 is prepared from 2via a disproportionation reaction where the by-product is [(TMEDA)·NaZn(tBu)3]. Another alkyl-diamido sodium zincate, [(TMEDA)·NaZn(DIBA)2(tBu)] 4 is synthesised by utilising diisobutylamine [DIBA(H)]. This reaction emphasises the generality of this disproportionation process. Complex 5 contains three cis-DMP ligands and is a tris-amido sodium magnesiate [(TMEDA)·NaMg(cis-DMP)3]. It is prepared by treating an equimolar mixture of butylsodium and dibutylmagnesium with three and one molar equivalents of cis-DMP(H) and TMEDA respectively, in hydrocarbon solution. By comparison of 1-5 with appropriate complexes from the literature, it has been possible to experimentally determine that the steric bulk of cis-DMP closely resembles that of DA but is considerably less bulky than 2,2,6,6-tetramethylpiperidide (TMP).",
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cis-2,6-Dimethylpiperidide: a structural mimic for TMP (2,2,6,6-tetramethypiperidide) or DA (diisopropylamide)? / Campbell, R.; Conway, B.; Garcia-Alvarez, P.; Kennedy, A.R.; Klett, J.; O'Hara, C.T.; Mulvey, R.E.; Robertson, G.; EPSRC (Funder).

In: Dalton Transactions, Vol. 39, 2010, p. 511-519.

Research output: Contribution to journalArticle

TY - JOUR

T1 - cis-2,6-Dimethylpiperidide: a structural mimic for TMP (2,2,6,6-tetramethypiperidide) or DA (diisopropylamide)?

AU - Campbell, R.

AU - Conway, B.

AU - Garcia-Alvarez, P.

AU - Kennedy, A.R.

AU - Klett, J.

AU - O'Hara, C.T.

AU - Mulvey, R.E.

AU - Robertson, G.

AU - EPSRC (Funder)

PY - 2010

Y1 - 2010

N2 - Four novel heterobimetallic ate complexes containing cis-2,6-dimethylpiperidide (cis-DMP) have been prepared and characterised. Two contain one cis-DMP ligand, namely the bisalkyl-amido lithium, and sodium zincates [(TMEDA)·MZn(cis-DMP)(tBu)2] (M = Li for 1, Na for 2). Both 1 and 2 are synthesised by co-complexation of the respective alkali metal amide with di-tert-butylzinc in the presence of a molar equivalent of N,N,N′,N′-tetramethylethylenediamine (TMEDA) in a hydrocarbon medium. The third complex, containing two cis-DMP ligands, is the alkyl-bisamido sodium zincate [(TMEDA)·NaZn(cis-DMP)2(tBu)] 3. Complex 3 is prepared from 2via a disproportionation reaction where the by-product is [(TMEDA)·NaZn(tBu)3]. Another alkyl-diamido sodium zincate, [(TMEDA)·NaZn(DIBA)2(tBu)] 4 is synthesised by utilising diisobutylamine [DIBA(H)]. This reaction emphasises the generality of this disproportionation process. Complex 5 contains three cis-DMP ligands and is a tris-amido sodium magnesiate [(TMEDA)·NaMg(cis-DMP)3]. It is prepared by treating an equimolar mixture of butylsodium and dibutylmagnesium with three and one molar equivalents of cis-DMP(H) and TMEDA respectively, in hydrocarbon solution. By comparison of 1-5 with appropriate complexes from the literature, it has been possible to experimentally determine that the steric bulk of cis-DMP closely resembles that of DA but is considerably less bulky than 2,2,6,6-tetramethylpiperidide (TMP).

AB - Four novel heterobimetallic ate complexes containing cis-2,6-dimethylpiperidide (cis-DMP) have been prepared and characterised. Two contain one cis-DMP ligand, namely the bisalkyl-amido lithium, and sodium zincates [(TMEDA)·MZn(cis-DMP)(tBu)2] (M = Li for 1, Na for 2). Both 1 and 2 are synthesised by co-complexation of the respective alkali metal amide with di-tert-butylzinc in the presence of a molar equivalent of N,N,N′,N′-tetramethylethylenediamine (TMEDA) in a hydrocarbon medium. The third complex, containing two cis-DMP ligands, is the alkyl-bisamido sodium zincate [(TMEDA)·NaZn(cis-DMP)2(tBu)] 3. Complex 3 is prepared from 2via a disproportionation reaction where the by-product is [(TMEDA)·NaZn(tBu)3]. Another alkyl-diamido sodium zincate, [(TMEDA)·NaZn(DIBA)2(tBu)] 4 is synthesised by utilising diisobutylamine [DIBA(H)]. This reaction emphasises the generality of this disproportionation process. Complex 5 contains three cis-DMP ligands and is a tris-amido sodium magnesiate [(TMEDA)·NaMg(cis-DMP)3]. It is prepared by treating an equimolar mixture of butylsodium and dibutylmagnesium with three and one molar equivalents of cis-DMP(H) and TMEDA respectively, in hydrocarbon solution. By comparison of 1-5 with appropriate complexes from the literature, it has been possible to experimentally determine that the steric bulk of cis-DMP closely resembles that of DA but is considerably less bulky than 2,2,6,6-tetramethylpiperidide (TMP).

KW - heterobimetallic ate complexes

KW - cis-DMP

KW - diisopropylamide

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