Preparation of 1,3‐diphosphabuta‐1,3‐dienes from sterically encumbered phosphaalkyne and phosphaethenyllithium

Ito, Shigekazu; Miyake, Hideaki; Sugiyama, Hiroki; Yoshifuji, Masaaki

doi:10.1002/hc.20104

Cited by 6 publications

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References 16 publications

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“…Using the sterically encumbered phosphaalkyne 2 , prepared by the 1,2‐elimination of disiloxane and the Fritsch‐Buttenberg‐Wiechell‐type rearrangement of phosphanylidenecarbene [Mes*P=C:],,,,, is useful to generate the phosphavinyl anion [RP=C(Li)Mes*] via the kinetically controlled regioselective nucleophilic addition of an organolithium reagent (RLi) ,. Prompt nucleophilic addition of the phosphavinyl anion [RP=C(Li)Mes*] to phosphaalkyne 2 affords 1,3‐diphosphacyclbuten‐4‐yl anion CBA via the [2+2] electrocyclization, of the anionic diphosphabutadiene intermediate (Scheme ) . Alkyllithiums, arylllithiums, silyllithiums, and lithium diisopropyl amide (LDA) are available to prepare the corresponding CBA .…”

Section: Chemistry Of 13‐diphosphacyclobuten‐4‐yl Anion (Cba)mentioning

confidence: 99%

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

Ito

2017

The Chemical Record

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Installing π-functional substituents on the skeletal phosphorus atoms of the air-tolerant 1,3-diphosphacyclobutane-2,4-diyl unit are promising for tuning the open-shell singlet P-heterocyclic chromophore. The sterically encumbered 1,3-diphosphaCycloButen-4-yl Anion (CBA), generated from the phosphorus-carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (S Ar) reaction, addition to arynes, and single-electron transfer (SET) process affording the corresponding P-arylated 1,3-diphosphacyclobutane-2,4-diyls. The photo-absorption and redox properties correlated with the effects of the aryl substituents on the 1,3-diphosphacyclobutane-2,4-diyl unit. The X-ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron-density distribution analysis. The electron-donating character of the P-heterocyclic chromophores induced the p-type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ ,3λ -diphosphete derivative was also developed.

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Section: Chemistry Of 13‐diphosphacyclobuten‐4‐yl Anion (Cba)mentioning

confidence: 99%

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

Ito

2017

The Chemical Record

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1,3‐Diphosphacyclobutene Cobalt Complexes

Rödl

Schwedtmann

Weigand

et al. 2019

Chemistry A European J

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The synthesis andc haracterization of rare 1,3-diphosphacyclobutene transition-metal complexes is described. Reactions of the cobalt-hydride complex [Co(P 2 C 2 tBu 2 ) 2 H] (G)w ith nBuLi, tBuLi, or PhLi afforded [Li-(solv) x {Co(h 3 -P 2 C 2 tBu 2 HR)(h 4 -P 2 C 2 tBu 2 )}] (1:R = nBu, (solv) x = (Et 2 O) 2 ; 2:R = tBu, (solv) x = (thf) 2 ; 3:R = Ph, (solv) x = (Et 2 O)(thf) 2 ), with an h 3 -coordinated 1,3-diphosphacyclobutene ligand as ar esult of organyl-anion attacka to ne of the phosphorus atoms of the bis(1,3-diphosphacyclobutadiene) backbone. In contrast to the reactions with PhLi, the arylmagnesium compounds p-tolyl magnesium chloride and p-fluorophenyl magnesiumbromide deprotonate [Co(P 2 C 2 tBu 2 ) 2 H] to give the magnesium salt [Mg(MeCN) 6 ] [Co(h 4 -P 2 C 2 tBu 2 ) 2 ] 2 (4), whichc ontainsabis(1,3-diphosphacyclobutadiene)-cobaltatea nion. The [Co(h 4 -P 2 C 2 tBu 2 ) 2 ] À anions are well separated from the octahedral [Mg(MeCN) 6 ] 2 + cationi nt he molecular structure of 4.C ompound 1 reacts with Me 3 SiCl to give neutral [Co(h 3 -P 2 C 2 tBu 2 HnBu)(h 4 -P 2 C 2 tBu 2 SiMe 3 )] (5,5 2% yield) with an SiMe 3 group attached to one of the Pa toms of the previously unfunctionalized backbone. Figure 1. Previously reported derivatizations of 1,3-diphosphacyclobutadiene complexes through the attack of nucleophiles. [7][8][9] [a] C. Rçdl,P rof. Dr.R.W olf Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.Figure 2. a) FunctionalizationofF by treatment with electrophiles (previous work): i) HCl·Et 2 O;ii)MeI ;iii)Ph 2 PCl ;b)synthesis of anionic 1,3-diphosphacyclobutenec omplexes 1-3 by addition of lithium organyls to G (this work).

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1,3‐Dipolarophile Character of an Extremely Bulky Phosphaalkyne MesC≡P (Mes = 2,4,6‐tBu₃C₆H₂) Leading to the Formation of 1,2,4‐Diazaphospholes with Unique Hydrogen Bonding Properties

2007

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[a][ ‡]Keywords: Heterocycles / Phosphaalkynes / Cycloaddition / Hydrogen bonds / DFT calculations / X-ray crystallography 2-(2,4,6-Tri-tert-butylphenyl)-1-phosphaethyne was allowed to react with trimethylsilyldiazomethane derivatives to afford the corresponding 1,2,4-diazaphospholes via [2+3] cycloaddition followed by H/SiMe 3 migration, in spite of the steric encumbrance of the substrates. The aromatic character of 1,2,4-diazaphosphole is indicated by the NMR spectroscopic data and the X-ray structure analysis as well as by theoretical

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Preparation of 1,3‐diphosphabuta‐1,3‐dienes from sterically encumbered phosphaalkyne and phosphaethenyllithium

Abstract: Kinetically stabilized 2

Cited by 6 publications

References 16 publications

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

1,3‐Diphosphacyclobutene Cobalt Complexes

1,3‐Dipolarophile Character of an Extremely Bulky Phosphaalkyne MesC≡P (Mes = 2,4,6‐tBu₃C₆H₂) Leading to the Formation of 1,2,4‐Diazaphospholes with Unique Hydrogen Bonding Properties

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Preparation of 1,3‐diphosphabuta‐1,3‐dienes from sterically encumbered phosphaalkyne and phosphaethenyllithium

Abstract: Kinetically stabilized 2

Cited by 6 publications

References 16 publications

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

1,3‐Diphosphacyclobutene Cobalt Complexes

1,3‐Dipolarophile Character of an Extremely Bulky Phosphaalkyne Mes*C≡P (Mes* = 2,4,6‐tBu3C6H2) Leading to the Formation of 1,2,4‐Diazaphospholes with Unique Hydrogen Bonding Properties

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1,3‐Dipolarophile Character of an Extremely Bulky Phosphaalkyne MesC≡P (Mes = 2,4,6‐tBu₃C₆H₂) Leading to the Formation of 1,2,4‐Diazaphospholes with Unique Hydrogen Bonding Properties