Mononuclear three-coordinate magnesium complexes of a highly sterically encumbered β-diketiminate ligand

M. Arrowsmith, B. Maitland, Gabriele Kociok-Köhn, A. Stasch, C. Jones, M.S. Hill

Research output: Contribution to journalArticle

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Abstract

The highly sterically encumbered chelating β-diketiminate ligand, [HC{C(Me)N(2,6-CHPh2-4-MeC6H2)}2]_, ArL_, has been used to prepare a series of heteroleptic three-coordinate magnesium complexes. Both the bis(imine) and imine-enamine tautomers of the ligand precursor, ArLH, as well as the diethyl ether adduct of the bromide complex [ArLMgBr(OEt2)], the monomeric methyl complex [ArLMgMe], the THF-solvated and unsolvated n-butylmagnesium complexes [ArLMgnBu(THF)] and [LMgBu], and the 1-hexynyl analogue [LMgCî -CBu] have been crystallographically characterized. Both n-butylmagnesium complexes showed remarkable stability in air, both in the solid state and in solution. Single crystals of the highly sensitive magnesium hydride, [ArLMgH], underwent partial hydrolysis by solid-state water diffusion to the isostructural hydroxide compound [LMgOH].

LanguageEnglish
Pages10543-10552
Number of pages10
JournalInorganic Chemistry
Volume53
Issue number19
Early online date9 Sep 2014
DOIs
StatusPublished - 6 Oct 2014

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Imines
Magnesium
imines
magnesium
Ligands
solid state
ligands
diethyl ether
tautomers
Chelation
Bromides
Hydrides
Ether
adducts
hydroxides
hydrides
hydrolysis
bromides
Hydrolysis
Single crystals

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Mononuclear three-coordinate magnesium complexes of a highly sterically encumbered β-diketiminate ligand. / Arrowsmith, M.; Maitland, B.; Kociok-Köhn, Gabriele; Stasch, A.; Jones, C.; Hill, M.S.

In: Inorganic Chemistry, Vol. 53, No. 19, 06.10.2014, p. 10543-10552.

Research output: Contribution to journalArticle

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abstract = "The highly sterically encumbered chelating β-diketiminate ligand, [HC{C(Me)N(2,6-CHPh2-4-MeC6H2)}2]_, ArL_, has been used to prepare a series of heteroleptic three-coordinate magnesium complexes. Both the bis(imine) and imine-enamine tautomers of the ligand precursor, ArLH, as well as the diethyl ether adduct of the bromide complex [ArLMgBr(OEt2)], the monomeric methyl complex [ArLMgMe], the THF-solvated and unsolvated n-butylmagnesium complexes [ArLMgnBu(THF)] and [LMgBu], and the 1-hexynyl analogue [LMgC{\^i} -CBu] have been crystallographically characterized. Both n-butylmagnesium complexes showed remarkable stability in air, both in the solid state and in solution. Single crystals of the highly sensitive magnesium hydride, [ArLMgH], underwent partial hydrolysis by solid-state water diffusion to the isostructural hydroxide compound [LMgOH].",
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AU - Arrowsmith, M.

AU - Maitland, B.

AU - Kociok-Köhn, Gabriele

AU - Stasch, A.

AU - Jones, C.

AU - Hill, M.S.

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N2 - The highly sterically encumbered chelating β-diketiminate ligand, [HC{C(Me)N(2,6-CHPh2-4-MeC6H2)}2]_, ArL_, has been used to prepare a series of heteroleptic three-coordinate magnesium complexes. Both the bis(imine) and imine-enamine tautomers of the ligand precursor, ArLH, as well as the diethyl ether adduct of the bromide complex [ArLMgBr(OEt2)], the monomeric methyl complex [ArLMgMe], the THF-solvated and unsolvated n-butylmagnesium complexes [ArLMgnBu(THF)] and [LMgBu], and the 1-hexynyl analogue [LMgCî -CBu] have been crystallographically characterized. Both n-butylmagnesium complexes showed remarkable stability in air, both in the solid state and in solution. Single crystals of the highly sensitive magnesium hydride, [ArLMgH], underwent partial hydrolysis by solid-state water diffusion to the isostructural hydroxide compound [LMgOH].

AB - The highly sterically encumbered chelating β-diketiminate ligand, [HC{C(Me)N(2,6-CHPh2-4-MeC6H2)}2]_, ArL_, has been used to prepare a series of heteroleptic three-coordinate magnesium complexes. Both the bis(imine) and imine-enamine tautomers of the ligand precursor, ArLH, as well as the diethyl ether adduct of the bromide complex [ArLMgBr(OEt2)], the monomeric methyl complex [ArLMgMe], the THF-solvated and unsolvated n-butylmagnesium complexes [ArLMgnBu(THF)] and [LMgBu], and the 1-hexynyl analogue [LMgCî -CBu] have been crystallographically characterized. Both n-butylmagnesium complexes showed remarkable stability in air, both in the solid state and in solution. Single crystals of the highly sensitive magnesium hydride, [ArLMgH], underwent partial hydrolysis by solid-state water diffusion to the isostructural hydroxide compound [LMgOH].

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