Synthesis of mixed alkali-metal-zinc enolate complexes derived from 2,4,6-trimethylacetophenone: new inverse crown structures

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Abstract

The solution and solid-state characterization of two new mixed alkali-metal−zinc enolate compounds is reported. These compounds are prepared by reaction of the relevant mixed-metal base [MZn(HMDS)3] (M = Na, K; HMDS = 1,1,1,3,3,3-hexamethyldisilazide) with a stoichiometric amount of the sterically demanding ketone 2,4,6-trimethylacetophenone. Thus, the new mixed-metal enolate compounds [Na2Zn2{OC(=CH2)Mes}6{OC(CH3)Mes}2] (2) and [K2Zn2{OC(=CH2)Mes}6(CH3Ph)2] (3) are obtained for M = Na, K, respectively. X-ray crystallographic studies reveal that both compounds adopt the same structural motif, which define them as inverse crown complexes, a cationic eight-membered [(MOZnO)2]2+ ring which hosts in its core two additional enolate ligands. Each Zn center is bonded to four anionic enolate ligands framing the structure, whereas the alkali metals form much weaker interactions with the oxygen atoms and complete their coodination sphere by bonding to a neutral molecule, an unenolised ketone for M = Na or toluene for M = K.
LanguageEnglish
Pages204-209
Number of pages6
JournalOrganometallics
Volume26
Issue number1
DOIs
Publication statusPublished - 5 Dec 2006

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Alkali Metals
Ketones
ketones
alkali metals
Zinc
zinc
Metals
Zinc compounds
zinc compounds
Ligands
ligands
metal compounds
Toluene
synthesis
toluene
oxygen atoms
Oxygen
solid state
X rays
Atoms

Keywords

  • enolate complexes
  • deprotonation
  • ketones
  • alkali-metal enolates
  • crown structures

Cite this

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title = "Synthesis of mixed alkali-metal-zinc enolate complexes derived from 2,4,6-trimethylacetophenone: new inverse crown structures",
abstract = "The solution and solid-state characterization of two new mixed alkali-metal−zinc enolate compounds is reported. These compounds are prepared by reaction of the relevant mixed-metal base [MZn(HMDS)3] (M = Na, K; HMDS = 1,1,1,3,3,3-hexamethyldisilazide) with a stoichiometric amount of the sterically demanding ketone 2,4,6-trimethylacetophenone. Thus, the new mixed-metal enolate compounds [Na2Zn2{OC(=CH2)Mes}6{OC(CH3)Mes}2] (2) and [K2Zn2{OC(=CH2)Mes}6(CH3Ph)2] (3) are obtained for M = Na, K, respectively. X-ray crystallographic studies reveal that both compounds adopt the same structural motif, which define them as inverse crown complexes, a cationic eight-membered [(MOZnO)2]2+ ring which hosts in its core two additional enolate ligands. Each Zn center is bonded to four anionic enolate ligands framing the structure, whereas the alkali metals form much weaker interactions with the oxygen atoms and complete their coodination sphere by bonding to a neutral molecule, an unenolised ketone for M = Na or toluene for M = K.",
keywords = "enolate complexes, deprotonation, ketones, alkali-metal enolates, crown structures",
author = "S.H. Baillie and E. Hevia and A.R. Kennedy and R.E. Mulvey",
year = "2006",
month = "12",
day = "5",
doi = "10.1021/om060878k",
language = "English",
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pages = "204--209",
journal = "Organometallics",
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publisher = "American Chemical Society",
number = "1",

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TY - JOUR

T1 - Synthesis of mixed alkali-metal-zinc enolate complexes derived from 2,4,6-trimethylacetophenone: new inverse crown structures

AU - Baillie, S.H.

AU - Hevia, E.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

PY - 2006/12/5

Y1 - 2006/12/5

N2 - The solution and solid-state characterization of two new mixed alkali-metal−zinc enolate compounds is reported. These compounds are prepared by reaction of the relevant mixed-metal base [MZn(HMDS)3] (M = Na, K; HMDS = 1,1,1,3,3,3-hexamethyldisilazide) with a stoichiometric amount of the sterically demanding ketone 2,4,6-trimethylacetophenone. Thus, the new mixed-metal enolate compounds [Na2Zn2{OC(=CH2)Mes}6{OC(CH3)Mes}2] (2) and [K2Zn2{OC(=CH2)Mes}6(CH3Ph)2] (3) are obtained for M = Na, K, respectively. X-ray crystallographic studies reveal that both compounds adopt the same structural motif, which define them as inverse crown complexes, a cationic eight-membered [(MOZnO)2]2+ ring which hosts in its core two additional enolate ligands. Each Zn center is bonded to four anionic enolate ligands framing the structure, whereas the alkali metals form much weaker interactions with the oxygen atoms and complete their coodination sphere by bonding to a neutral molecule, an unenolised ketone for M = Na or toluene for M = K.

AB - The solution and solid-state characterization of two new mixed alkali-metal−zinc enolate compounds is reported. These compounds are prepared by reaction of the relevant mixed-metal base [MZn(HMDS)3] (M = Na, K; HMDS = 1,1,1,3,3,3-hexamethyldisilazide) with a stoichiometric amount of the sterically demanding ketone 2,4,6-trimethylacetophenone. Thus, the new mixed-metal enolate compounds [Na2Zn2{OC(=CH2)Mes}6{OC(CH3)Mes}2] (2) and [K2Zn2{OC(=CH2)Mes}6(CH3Ph)2] (3) are obtained for M = Na, K, respectively. X-ray crystallographic studies reveal that both compounds adopt the same structural motif, which define them as inverse crown complexes, a cationic eight-membered [(MOZnO)2]2+ ring which hosts in its core two additional enolate ligands. Each Zn center is bonded to four anionic enolate ligands framing the structure, whereas the alkali metals form much weaker interactions with the oxygen atoms and complete their coodination sphere by bonding to a neutral molecule, an unenolised ketone for M = Na or toluene for M = K.

KW - enolate complexes

KW - deprotonation

KW - ketones

KW - alkali-metal enolates

KW - crown structures

U2 - 10.1021/om060878k

DO - 10.1021/om060878k

M3 - Article

VL - 26

SP - 204

EP - 209

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

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ER -