Synthesis, structure and theoretical studies of the hydrido inverse crown [K2Mg2(NiPr2)(4)(mu-H)(2)center dot(toluene)(2)]: a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge

P.C. Andrikopoulos, D.R. Armstrong, A.R. Kennedy, R.E. Mulvey, C.T. O'Hara, R.B. Rowlings

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Abstract

Reaction of benzylpotassium, n,s-dibutylmagnesium and diisopropylamine in boiling toluene produces a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge, in [K2Mg2(NiPr2)(4)(mu-H)(2).(toluene)(2)] (1). In an effort to rationalise the formation of 1, a series of DFT calculations were performed. This report of 1 establishes the first isostructural pair of Na and K complexes solvated by toluene to be reported in the Cambridge Crystallographic Database. In comparison with its previously reported Na analogue, 2, the metal-arene centroid distances are considerably shorter (by 0.159 Angstrom) in the new complex reported here. It was found that a hydrocarbon solution of 1 is capable of reducing benzophenone to benzhydrol in moderate yields (74%).
LanguageEnglish
Pages3354-3362
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2003
Issue number18
DOIs
Publication statusPublished - 26 Sep 2003

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Toluene
Hydrides
Magnesium
Hydrogen
Hydrocarbons
Discrete Fourier transforms
Boiling liquids
Metals

Keywords

  • potassium
  • magnesium
  • N ligands
  • hydride ligands
  • density functional calculations

Cite this

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title = "Synthesis, structure and theoretical studies of the hydrido inverse crown [K2Mg2(NiPr2)(4)(mu-H)(2)center dot(toluene)(2)]: a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge",
abstract = "Reaction of benzylpotassium, n,s-dibutylmagnesium and diisopropylamine in boiling toluene produces a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge, in [K2Mg2(NiPr2)(4)(mu-H)(2).(toluene)(2)] (1). In an effort to rationalise the formation of 1, a series of DFT calculations were performed. This report of 1 establishes the first isostructural pair of Na and K complexes solvated by toluene to be reported in the Cambridge Crystallographic Database. In comparison with its previously reported Na analogue, 2, the metal-arene centroid distances are considerably shorter (by 0.159 Angstrom) in the new complex reported here. It was found that a hydrocarbon solution of 1 is capable of reducing benzophenone to benzhydrol in moderate yields (74{\%}).",
keywords = "potassium, magnesium, N ligands, hydride ligands, density functional calculations",
author = "P.C. Andrikopoulos and D.R. Armstrong and A.R. Kennedy and R.E. Mulvey and C.T. O'Hara and R.B. Rowlings",
year = "2003",
month = "9",
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TY - JOUR

T1 - Synthesis, structure and theoretical studies of the hydrido inverse crown [K2Mg2(NiPr2)(4)(mu-H)(2)center dot(toluene)(2)]

T2 - European Journal of Inorganic Chemistry

AU - Andrikopoulos, P.C.

AU - Armstrong, D.R.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - O'Hara, C.T.

AU - Rowlings, R.B.

PY - 2003/9/26

Y1 - 2003/9/26

N2 - Reaction of benzylpotassium, n,s-dibutylmagnesium and diisopropylamine in boiling toluene produces a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge, in [K2Mg2(NiPr2)(4)(mu-H)(2).(toluene)(2)] (1). In an effort to rationalise the formation of 1, a series of DFT calculations were performed. This report of 1 establishes the first isostructural pair of Na and K complexes solvated by toluene to be reported in the Cambridge Crystallographic Database. In comparison with its previously reported Na analogue, 2, the metal-arene centroid distances are considerably shorter (by 0.159 Angstrom) in the new complex reported here. It was found that a hydrocarbon solution of 1 is capable of reducing benzophenone to benzhydrol in moderate yields (74%).

AB - Reaction of benzylpotassium, n,s-dibutylmagnesium and diisopropylamine in boiling toluene produces a rare example of a molecular magnesium hydride with a Mg-(mu-H)(2)-Mg double bridge, in [K2Mg2(NiPr2)(4)(mu-H)(2).(toluene)(2)] (1). In an effort to rationalise the formation of 1, a series of DFT calculations were performed. This report of 1 establishes the first isostructural pair of Na and K complexes solvated by toluene to be reported in the Cambridge Crystallographic Database. In comparison with its previously reported Na analogue, 2, the metal-arene centroid distances are considerably shorter (by 0.159 Angstrom) in the new complex reported here. It was found that a hydrocarbon solution of 1 is capable of reducing benzophenone to benzhydrol in moderate yields (74%).

KW - potassium

KW - magnesium

KW - N ligands

KW - hydride ligands

KW - density functional calculations

UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1099-0682c

U2 - 10.1002/ejic.200300414

DO - 10.1002/ejic.200300414

M3 - Article

VL - 2003

SP - 3354

EP - 3362

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 18

ER -