Abstract
| Language | English |
|---|---|
| Pages | 5875-5887 |
| Number of pages | 13 |
| Journal | Dalton Transactions |
| Volume | 44 |
| Issue number | 12 |
| Early online date | 17 Feb 2015 |
| DOIs | |
| Publication status | Published - 28 Mar 2015 |
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Keywords
- sodium monoamido-bisalkylzincate [
- crystalline complexes
- NMR spectroscopy
- X-ray crystallography
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Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA) : benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex. / Kennedy, Alan R.; Mulvey, Robert E.; Ramsay, Donna L.; Robertson, Stuart D.
In: Dalton Transactions, Vol. 44, No. 12, 28.03.2015, p. 5875-5887.Research output: Contribution to journal › Article
TY - JOUR
T1 - Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA)
T2 - Dalton Transactions
AU - Kennedy, Alan R.
AU - Mulvey, Robert E.
AU - Ramsay, Donna L.
AU - Robertson, Stuart D.
PY - 2015/3/28
Y1 - 2015/3/28
N2 - Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.
AB - Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.
KW - sodium monoamido-bisalkylzincate [
KW - crystalline complexes
KW - NMR spectroscopy
KW - X-ray crystallography
UR - http://www.scopus.com/inward/record.url?scp=84924873681&partnerID=8YFLogxK
U2 - 10.1039/c5dt00247h
DO - 10.1039/c5dt00247h
M3 - Article
VL - 44
SP - 5875
EP - 5887
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 12
ER -