A direct synthesis of 1,3-bis(bromomagnesio)propane

Seetz, J. W. F. L.; Hartog, F.; Bohm, Howard; Blomberg, C.; Akkerman, Otto S.; Bickelhaupt, F.

doi:10.1016/s0040-4039(00)87142-7

Cited by 34 publications

(15 citation statements)

References 16 publications

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“…This suggests that the identity of the leaving group does not play a significant role in the occurring side reaction and that it may be a problem with the synthetic strategy in general. A possible alternative to circumvent this could involve an Umpolung-type reversal of polarities, generating di-Grignards from 1,3-dihalides as the nucleophile to attack chlorophosphine electrophiles instead …”

Section: Resultsmentioning

confidence: 56%

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gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

et al. 2019

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A series of palladium complexes with C 3 -bridged bidentate bis(diphenylphosphino)propane ligands with substituents of varying steric bulk at the central carbon have been synthesized. The size of the gem-dialkyl substituents affects the C−C−C bond angles within the ligands and consequently the P−M−P ligand bite angles. A combination of solid-state X-ray diffraction (XRD) and density functional theory (DFT) studies has shown that an increase in substituent size results in a distortion of the 6-membered metal−ligand chair conformation toward a boat conformation, to avoid bond angle strain. The influence of the gem-dialkyl effect on the catalytic performance of the complexes in palladium-catalyzed hydroformylation of 1-octene has been investigated. While hydroformylation activity to nonanal decreases with increasing size of the gem-dialkyl substituents, a change in chemoselectivity toward nonanol via reductive hydroformylation is observed.

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Section: Resultsmentioning

confidence: 56%

“…A possible alternative to circumvent this could involve an Umpolung-type reversal of polarities, generating di-Grignards from 1,3-dihalides as the nucleophile to attack chlorophosphine electrophiles instead. 30 2.4. Palladium Complexes.…”

Section: Resultsmentioning

confidence: 99%

gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

et al. 2019

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“…Both of the reactive di‐substituted DSCB monomers, 1,3‐dichloro‐DSCB and 1,3‐diethoxy‐DSCB, can be obtained with high purity from commercially available starting materials (98%‐99%). On the other hand, the preparation of the di‐Grignard alkanes from dihaloalkanes have been reported by many research groups to have yields around 80%, in general . The side reactions in the Grignard reaction of alkylhalides mainly include inter‐ or intra(cyclization)‐ molecular Wurtz coupling and β‐elimination, which are observed especially at elevated temperatures and when the dihaloalkane is added too quickly or in excess.…”

Section: Resultsmentioning

confidence: 99%

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Liu

Rathore

Dubois

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Alkylene‐ and arylene‐bridged cyclolinear polycarbosilanes (CLPCS) with 1,3‐disilacyclobutane (DSCB) rings incorporated in the main chain of the polymer were prepared by polycondensation between corresponding di‐functional DSCB derivatives and di‐Grignard reagents. Well‐defined, low molecular weight (Mn = 3–5K; DP = 17–26), hexylene‐ and phenylene‐bridged CLPCS polymers were obtained without appreciable ring opening of the DSCB rings. Large exothermic peaks were observed in the DSC for these CLPCSs, which indicated, along with the IR spectra, that crosslinking occurred on heating to about 250 °C via the ring opening of the embedded, alternating, DSCB rings. Moreover, PB‐CLPCS undergoes photochemically induced crosslinking on UV irradiation to form crosslinked polycarbosilane network films. The spin‐cast, cured, films of these CLPCSs exhibit relatively low dielectric constants and promising thermal and mechanical properties for applications in electronics, for example, directly UV‐photoimprinted low‐k dielectrics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1547–1557

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“…The reaction of these substrates with excess magnesium turnings in THF gave solutions of the corresponding primary and tertiary di-Grignard complexes with good (78–90%) to moderate (35–42%) yields (Scheme ). This protocol is not suitable for the preparation of analogous derivatives with short alkanediide fragments (C 2 –C 3 ) . A different strategy employing the mercury derivatives according to Costa and Whitesides was rejected due to toxicity reasons.…”

Section: Resultsmentioning

confidence: 99%

Magnesiacycloalkanes with Different Ring Sizes

et al. 2016

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Di-Grignard compounds are prepared via the direct synthesis of magnesium with Br2C{Si(CH3)3}2, α,ω-dihalides of XCH2YCH2X (X: Cl, Br; Y: Si(CH3)2, (CH2) n with n = 4, 5, 6), and with ClC(CH3)2(CH2) n (CH3)2CCl (n = 3, 4) in tetrahydrofuran (THF) or diethyl ether. After removal of the sparingly soluble magnesium halides after addition of 1,4-dioxane (dx) the corresponding magnesium alkanediides remain in solution. Only the geminal di-Grignard complex (BrMg)2(μ-C{Si(CH3)3}2) forms the corresponding dioxane adduct [{(dx)2MgBr}2(μ-C{Si(CH3)3}2)] (1). The magnesium alkanediides can be recrystallized from THF and characterized with X-ray crystallography and NMR spectroscopy. Preferably dinuclear rings of the types [(thf)2Mg(μ-CH2-Y-CH2)}2] (Y: Si(CH3)2 (2), (CH2)6 (5)) and [({thf}2Mg{μ-C(CH3)2(CH2)4C(CH3)2})2] (7) crystallize. From a 1 M solution the strand-like coordination polymer [({thf}2Mg{μ-(CH2)6})∞] (3) precipitates. Only [(thf)2Mg{C(CH3)2(CH2)3(CH3)2C}] (6) crystallizes as a mononuclear compound. The NMR spectra of 2, 3, 5, and 6 show only one set of resonances for the alkanediyl moieties in [D8]THF solutions. The NMR spectra of 7 showed also at 50 °C two signal sets with the intensity ratios depending on the measurement temperature. Complex 7 shows a temperature-dependent monomer–dimer equilibrium in THF solution.

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A direct synthesis of 1,3-bis(bromomagnesio)propane

Cited by 34 publications

References 16 publications

gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Magnesiacycloalkanes with Different Ring Sizes

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