Sekundäre Phosphinchalkogenide. VII. Synthese von Bis(tert.‐butylphosphino)ethan, ButHPCH2CH2PHBut, und 1‐tert.‐Butylphosphino‐2‐diphenylphosphino‐ethan, Ph2PCH2CH2PHBut, sowie deren sekundäre Phosphinchalkogenide

Weisheit, R.; Stendel, R.; Messbauer, B.; Langer, Carl; Walther, B.

doi:10.1002/zaac.19835040919

Cited by 16 publications

(13 citation statements)

References 10 publications

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“…14,15,16,17 Some early literature precedent, however, suggested the ability to selectively mono-functionalize 1,2bis(dichlorophosphino)ethane (1) using larger cyclohexylor tert-butyl-substituted Grignard reagents, providing access to 1,2-bis-((chloro)alkyl)phosphino)ethane as a mixture of three (two racemic and one meso) isomers. 18 Although this pathway provides a mixture of chirogenic diphosphines, it nonetheless presents a practical means (and an initial testing ground) to access pendant diboranylcontaining diphosphine ligands. To our knowledge, these precursors have not been previously used to prepare diphosphine ligand precursors.…”

Section: Resultsmentioning

confidence: 99%

“…The identity of the major isomer ((±)-rac or -meso) is unknown, but is likely the more stable (±)-rac-isomer. 18 For this and other diphosphine moieties described herein, 31 P NMR spectroscopy was used to determine the relative ratio of isomers (e.g., dP = 130.6 and 128.0 ppm for (±)-rac/meso-2). Density functional theory (DFT) 19 optimizations were also performed; DLPNO-CCSD(T) calculations 20 provide a negligible (DGrel = 1.7 kcal mol -1 ) energetic difference between (±)-rac-and meso-2, consistent with observation of both.…”

Section: Resultsmentioning

confidence: 99%

“…(±)-rac/meso-1,2-bis-((chloro)tertbutyl)phosphino)ethane 18 [CAS: 89227-46-3] ((±)-rac/meso-2; C10H22Cl2P2, MW = 274 g/mol): In the glovebox, Cl2P(CH2)2PCl2 (1.29 g, 0.0056 mol) was added to a 250 mL reaction flask equipped with a stir bar and 100 mL Et2O. The reaction flask was cycled onto a Schlenk line and tertbutylmagnesium chloride (5.6 mL, 0.011 mol, 2 equiv.)…”

Section: Preparation Of Compoundsmentioning

confidence: 99%

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Racemic and Meso Diastereomers of a P-Chirogenic Diboranyldiphosphinoethane

Austen

Sharma

Zurakowski

et al. 2022

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Diphosphine ligands have enjoyed great success as sup-porting moieties for transition elements, where modifica-tion of both primary and secondary coordination sphere has been shown to illicit differences in chemical reactivi-ty. This work describes a new family of such ligands con-structed from the previously reported scaffold, (±)-rac/meso-(t-Bu)ClP-CH2CH2-PCl(t-Bu) that bears bulky tert-butyl substituents. Reaction of this precursor with allyl magnesium chloride and subsequent hydroboration using HBCy2 (Cy = cyclohexyl) provides access to a di-boranyldiphosphinoethane – the first in a class of ligands having two electrophilic boranes in their secondary coor-dination sphere. As a testing ground for coordination, these motifs (and their allyl precursor) have been in-stalled at Ni(0) using [Ni(COD)2] (COD = 1,5-cyclooctadiene) in order to determine methods for clean installation. Product stereochemical outcomes are in some cases complicated and have been determined by NMR spectroscopic and crystallographic means. Density func-tional theory optimizations and accurate DLPNO-CCSD(T) energy calculations were also performed to sup-port structural assignment.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Preparation Of Compoundsmentioning

confidence: 99%

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Racemic and Meso Diastereomers of a P-Chirogenic Diboranyldiphosphinoethane

Austen

Sharma

Zurakowski

et al. 2022

Preprint

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“…Mass spectra (EI) were recorded on a Bell and Howell 21-491 instrument, and elemental analyses were determined on a Perkin-Elmer 2400 analyzer. 1,2-Bis(alkylphosphino)benzenes and 1,2-bis( tert- butylphosphino)ethane were prepared according to the literature methods. Al 2 Me 6 and GaMe 3 were purchased commercially (Aldrich).…”

Section: Methodsmentioning

confidence: 99%

Use of Chelating Diphosphines To Prepare New Phosphido Clusters of Aluminum and Gallium

et al. 1996

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Novel phosphido cluster complexes of formula (Me2M)4(μ-(1,2-PR)2C6H4)2 (M = Al, R = Me (1); M = Ga, R = t-Bu (2)) result when the chelating diphosphine ligand 1,2-bis(alkylphosphino)benzene is mixed with trialkylaluminum and -gallium reagents. When the potentially chelating ligand 1,2-bis(tert-butylphosphino)ethane is mixed with 2 equiv of AlMe3 under the same conditions, the secondary phosphine bis-adduct complex Me3Al·PH(t-Bu)CH2CH2(t-Bu)HP·AlMe3 (3) is formed.

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“…10, 11 At the same time, methods for the preparation of bis phosphine sul fides, as a rule, are multistep and laborious and are based on toxic phosphorus halides and organometallic reagents. 12 One of the most convenient approaches to the synthesis of tertiary bis phosphine chalcogenides is the reaction of nucleophilic addition of two molecules of secondary phos phine chalcogenide to acetylenes. This reaction is at the time under intensive study on the example of "activated" acetylenes with the triple bond bearing electron with drawing groups.…”

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confidence: 99%

Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

et al. 2009

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Secondary phosphine sulfides react with acetylene and methylacetylene in the system КOH-DMSO (50 °C, 2-3 h) to form the corresponding tertiary bis phosphine sulfides in high yield (up to 97%). Specific features of the NMR spectra ( 1 H, 13 C, and 31 P) of compounds obtained are discussed.Bis phosphine sulfides are under intensive study as efficient polydentate ligands for the design of metal com plex catalysts, 1-4 antipyrenes, 5 intermediate products for the development of fluorescent and electroluminescent sensors, 6 as well as promising solvents and intermediates for the preparation of semiconducting nanomaterials. 7 Bis phosphine sulfides with chiral centers are of particular value. 8 Reduction of the latter leads to the corresponding optically active bis phosphines, 9 which are widely used in the catalytic stereoselective synthesis. 10,11 At the same time, methods for the preparation of bis phosphine sul fides, as a rule, are multistep and laborious and are based on toxic phosphorus halides and organometallic reagents. 12 One of the most convenient approaches to the synthesis of tertiary bis phosphine chalcogenides is the reaction of nucleophilic addition of two molecules of secondary phos phine chalcogenide to acetylenes. This reaction is at the time under intensive study on the example of "activated" acetylenes with the triple bond bearing electron with drawing groups. 13-16 The reaction of acetylene and its first and the most available homolog (methylacetylene) with secondary phosphine sulfides has not been imple mented so far. Moreover, it was reported 13 that diphenyl phosphine sulfide does not react with electron saturated acetylenes (hexyne, phenylacetylene) under nucleophilic conditions, for example, in the system КОH-H 2 OMeCN.In the present work, in order to develop a straight forward method for the synthesis of new bis phosphine sulfides, the reaction of nucleophilic addition of second ary phosphine sulfides 1a,b, easily available from styrenes, * Dedicated to Academician A. I. Konovalov in honor of his 75th anniversary. red phosphorus, and elementary sulfur, to acetylene and methylacetylene has been studied. 17,18 Experiments showed that virtually no reaction takes place in the system КОH-THF. At the same time, when superbasic catalytic system КОH-DMSO 19 was used, the nucleophilic addition of two molecules of secondary phos phine sulfide proceeds efficiently at mild temperatures (50 °C, 2-3 h) under pressure of acetylene (autoclave, the initial pressure of 14 atm) or in the channel system (in the case of methylacetylene) with the formation of bis adducts 2a-c in high yield (Scheme 1). Scheme 1R 1 = R 2 = H (a); R 1 = Bu t , R 2 = H (b); R 1 = H, R 2 = Me (c)

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Sekundäre Phosphinchalkogenide. VII. Synthese von Bis(tert.‐butylphosphino)ethan, Bu^tHPCH₂CH₂PHBu^t, und 1‐tert.‐Butylphosphino‐2‐diphenylphosphino‐ethan, Ph₂PCH₂CH₂PHBu^t, sowie deren sekundäre Phosphinchalkogenide

Cited by 16 publications

References 10 publications

Racemic and Meso Diastereomers of a P-Chirogenic Diboranyldiphosphinoethane

Racemic and Meso Diastereomers of a P-Chirogenic Diboranyldiphosphinoethane

Use of Chelating Diphosphines To Prepare New Phosphido Clusters of Aluminum and Gallium

Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

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