Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe<sub>3</sub>}<sub>2</sub>)Br(thf)

Day, Benjamin M.; Coles, Martyn P.

doi:10.1002/ejic.201000810

Cited by 8 publications

(5 citation statements)

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“…A Grignard compound containing similar structural units, PrMgCl 2 (THF) 2 (Pr = propenyl), is found in the literature . Compounds having the open dicubane-like structure have been reported previously in the literature. − These previously reported structures differ from the present stoichiometric complex, as they contain only four Mg atoms instead of six Mg atoms in [Mg 3 Cl 5 (THF) 4 Bu] 2 . The theoretical THF/Mg molar ratio in [Mg 3 Cl 5 (THF) 4 Bu] 2 is 1.33, while the analyzed THF/Mg ratio in sample 6 was 1.21.…”

Section: Resultssupporting

confidence: 60%

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)

et al. 2013

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The influence of the electron donor tetrahydrofuran (THF) on the formation of the crystalline morphology of MgCl 2 was studied. MgCl 2 was synthesized from magnesium and 1-chlorobutane in the presence of THF with the THF/Mg molar ratio ranging from 0.063 to 2.0. With the highest amounts of THF crystalline particles were formed, as evidenced from scanning electron microscopy images. The X-ray structure analysis of these single crystals revealed the new organometallic Mg compound [Mg 3 Cl 5 (THF) 4 Bu] 2 (Bu = n-butyl), which has an open dicubanelike structure with four octahedrally and two tetrahedrally coordinated Mg atoms. The compound also contains two butyl groups directly bound to the Mg atoms at the opposite corners of the dicubane structure. With the lowest THF amounts, structurally disordered MgCl 2 /THF complexes were formed. The transition from single crystals toward particles with an amorphous morphology appeared to occur through an intermediate type of morphology with a three-dimensional network structure. The network structure is formed from a thin (30−100 nm) fiberlike MgCl 2 /THF material. Infrared and solid-state 13 C nuclear magnetic resonance spectroscopy measurements revealed different types of Mg sites present in the MgCl 2 /THF complexes.

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Section: Resultssupporting

confidence: 60%

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)

et al. 2013

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“…Only a handful of terminal magnesium-phosphanide complexes have been reported, including three examples of a terminal bis-trimethysilyl phosphanide ligand [38,43,44] and one example of a phenyl phosphanide complex, [37] although there have been several reports of bridging phosphanide ligands. [44][45][46] This is the first example of a diphenylphosphanide ligand on a magnesium centre. The closest analogy is the isostructural calcium complex [(BDI)Ca(PPh 2 )(THF)], which undergoes Schlenk-like redistribution to homoleptic calcium complexes [(BDI) 2 Ca] and [Ca(PPh 2 ) 2 (THF) 2 ].…”

Section: Discussionmentioning

confidence: 93%

Reactivity of β-Diketiminato Magnesium Alkyl Complexes: Heterocumulenes and Phosphanes

2015

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Heteroleptic b-diketiminate/amidinate magnesium complexes {(BDI)Mg[MeC(NCy) 2 ]} and {(BDI)Mg[BnC(NCy) 2 ]} (Bn ¼ CH 2 C 6 H 5 ; BDI ¼ {[N(2,6-i Pr 2 C 6 H 3 )C(Me)] 2 CH}) were synthesised by treatment of [(BDI)MgR(THF)] (R ¼ Me, Bn) with dicyclohexylcarbodiimide. Rare terminal magnesium phosphanide complexes [(BDI)Mg(PR 0 2 )(THF)] (R 0 ¼ Cy, Ph) were synthesised through prolonged exposure of [(BDI)MgMe(THF)] with di-substituted phosphines. Spectroscopic and structural details of these complexes will be discussed. * This manuscript is dedicated to Kappa, who was always an inspiration for Sussex chemists.Ar N N Ar L-endo L-exo Mg Fig. 1. The two different environments of the non-b-diketiminate ligands on [(BDI)MgL 2 ] complexes. CSIRO PUBLISHING Aust. J. Chem. 2015, 68, 635-640 http://dx.

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“…This approach was used rather than the carbodiimide insertion route that has successfully been employed by Hill 38,39 and Westerhausen 40 to synthesize phosphaguanidinate compounds of Ca, Sr and Ba, primarily due to the lack of availability of suitable magnesium phosphanides. 41 Compounds 6 and 8 were isolated in good yield and characterized by 1 H, 13 C and 31 P NMR spectroscopy. The yield for compound 7 was not optimized and spectroscopic data were not obtained; subsequent reactions generated this compound in situ.…”

Section: Synthesismentioning

confidence: 99%

Catalytic bond forming reactions promoted by amidinate, guanidinate and phosphaguanidinate compounds of magnesium

et al. 2014

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The synthesis and catalytic properties of a series of magnesium compounds consisting of monoanionic, N,N'-chelating ligands (N∩N = amidinates, guanidinates, phosphaguanidinates) is reported. The compounds were synthesized by (i) insertion of a carbodiimide into an existing Mg-C or Mg-N bond, or (ii) protonolysis of an organomagnesium compound by a neutral pre-ligand. Structural analyses of mono- or bis-(chelate) compounds with general formula Mg(N∩N)X(L)n and Mg(N∩N)2(L)n (X = halide, aryloxide, amide; L = Et2O, THF; n = 0, 1 or 2) have been performed and the influence that the ligand substituent patterns have on the solid-state structures has been probed. Selected examples of the compounds were tested as (pre)catalysts for the polymerization of lactide, the dimerization of aldehydes and the hydroacetylenation of carbodiimides.

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Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe₃}₂)Br(thf)

Abstract: The novel phospha-Grignard reagent Mg(PRЈ 2 )X(thf) [RЈ = SiMe 3 , X = Br (1)/Me (1Ј)] was synthesized and structurally characterized as the phosphide-bridged dimer [1] 2 . The potential for this compound to behave as a redox-friendly phos-

Cited by 8 publications

References 18 publications

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)

Reactivity of β-Diketiminato Magnesium Alkyl Complexes: Heterocumulenes and Phosphanes

Catalytic bond forming reactions promoted by amidinate, guanidinate and phosphaguanidinate compounds of magnesium

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Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe3}2)Br(thf)

Abstract: The novel phospha-Grignard reagent Mg(PRЈ 2 )X(thf) [RЈ = SiMe 3 , X = Br (1)/Me (1Ј)] was synthesized and structurally characterized as the phosphide-bridged dimer [1] 2 . The potential for this compound to behave as a redox-friendly phos-

Cited by 8 publications

References 18 publications

A Single-Crystal Model for MgCl2–Electron Donor Support Materials: [Mg3Cl5(THF)4Bu]2 (Bu = n-Butyl)

A Single-Crystal Model for MgCl2–Electron Donor Support Materials: [Mg3Cl5(THF)4Bu]2 (Bu = n-Butyl)

Reactivity of β-Diketiminato Magnesium Alkyl Complexes: Heterocumulenes and Phosphanes

Catalytic bond forming reactions promoted by amidinate, guanidinate and phosphaguanidinate compounds of magnesium

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Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe₃}₂)Br(thf)

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)

A Single-Crystal Model for MgCl₂–Electron Donor Support Materials: [Mg₃Cl₅(THF)₄Bu]₂ (Bu = n-Butyl)