Intercepting a Transient Phosphino‐Arsinidene

Hinz, Alexander; Hansmann, Max M.; Bertrand, Guy; Goicoechea, José M.

doi:10.1002/chem.201802175

Cited by 31 publications

(23 citation statements)

References 52 publications

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“…The As−P bond length is 2.2152(6) Å, which is almost identical with the As−P distances reported for the cationic C 2 ‐symmetric compound [(IDipp)PAsP(IDipp)]Cl (2.203(1) Å) and for the bimetallic AsP complex F (2.2324(13) Å) . Slightly longer bonds were found for other related NHC arsenic–phosphorus systems, for example 2.3133(4) Å in [(SIMes)PAs( t Bu) 2 ] or 2.3552(6) Å in the IDipp adduct of a transient phosphino–arsinidene (SIMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidin‐2‐ylidene) …”

Section: Figurementioning

confidence: 99%

“…[17] Slightly longer bonds were found for other relatedN HC arsenic-phosphorus systems, for example 2.3133(4) in [(SIMes)PAs(tBu) 2 ] [23] or 2.3552(6) in the IDipp adduct of at ransient phosphino-arsinidene (SIMes = 1,3bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene). [24] Reduction of 3 with two equivalents of potassium graphite (KC 8 )i nT HF afforded [(IMes)AsP(IDipp)] (4)w hich was isolated as ad ark red solid in 37 %y ield (Scheme 1). The 31 PNMR spectrum (in C 6 D 6 ,F igure S8, Supporting Information) showeda broad signal at À60.6 ppm, whichl ies between the chemical shifts established for the homoleptic diphosphoruss pecies [(IDipp)P 2 (IDipp)] (B, À52.4 ppm) and [(IMes)P 2 (IMes)] (À73.6 ppm), [6] whereas the heteroleptic congener [(IMes)-P 2 (IDipp)] afforded two doubletsw ith similar chemical shifts at À63.1 and À59.4 ppm ( 1 J PP = 249 Hz).…”

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confidence: 99%

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Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺

Doddi

Bockfeld

Zaretzke

et al. 2019

Chemistry A European J

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Arsenicm onophosphide (AsP) species supported by two different N-heterocyclic carbenes were prepared by reaction of (IDipp)PSiMe 3 (1)( IDipp = 1,3-bis(2,6diisopropylphenyl)imidazolin-2-ylidene) with (IMes)AsCl 3 (2)( IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) to afford the dichloride [(IMes)As(Cl)P(IDipp)]Cl (3), which upon reduction with KC 8 furnished heteroleptic [(IMes)AsP(IDipp)] (4). The corresponding mono-and dications [(IMes)AsP(IDipp)][PF 6 ], [5]PF 6 ,a nd [(IMes)AsP(I-Dipp)][GaCl 4 ] 2, [6] [GaCl 4 ] 2 ,r espectively,w ere prepared by one-electron oxidation of 4 with ferrocenium hexafluorophosphate, [Fc]PF 6, or by chloride abstraction from 3 with two equivalentso fG aCl 3 ,r espectively.C ompounds 4-6 represent rare examples of heterodiatiomic interpnictogen compounds, and X-ray crystal structure determinations together with density functional theory (DFT) calculations reveal ac onsecutive shortening of the AsÀPb ond lengths and increasing bond order, in agreement with the presence of an arsenic-phosphorus single bond in 4 and a double bond in 6 2+ + .T he EPR signal of the cationic radical [5] + + C indicates as ymmetric spin distribution on the AsP moiety through strongh yperfine coupling with the 75 As and 31 Pn uclei.Carbene stabilization of diatomic allotropes has been among the most successful applicationso fN -heterocyclic carbenes (NHC) in main-group element chemistry, [1] with the homodinuclear systems [(IDipp)E 2 (IDipp)] (E = B, [2] Si, [3] Ge, [4] Sn, [5] P, [6] As, [7] IDipp = bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) representing the most prominente xamples. In contrast, heterodinuclear species are rare, and to the best of our knowledge,t he heteroleptic carbene-stabilized "phosphorus mononitride" A and its radicalc ation (PN + +· )r epresent the only compounds, in which ad iatomic moiety consisting of two different p-blocke lements is supported by two carbene ligands ( Figure 1). [8] The controlled synthesis of such species requires amodular approach for assembling the two different (NHC)Es ides, and we have recently establisheds uch ap rotocols uccessfully for the preparation of the heteroleptic dicarbene-diphosphorus species [(IMes)P 2 (IDipp)] (B,I Mes = bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene), [9] which represents ah ybrid of the previously reported homoleptic congeners [(IMes)P 2 (IMes)] (C)a nd [(IDipp)P 2 (IDipp)] (D). [6] Moreover,i nasimilar manner as described for D and also for the analogous diarsenic compound [(IDipp)As 2 (IDipp)] (E), [10,11] the corresponding radical cation [(IMes)P 2 (IDipp)] + + C and dication [(IMes)P 2 (IDipp)] 2+ + were also prepared and structurally characterized. Notably,t he heteroleptic natureo ft his system allowed for establishing phosphorusphosphorus coupling in the diamagnetic neutrala nd dicationic forms. [9] We reasoned that as imilarm odulara pproach could give accesst oh eterodiatomic Group 15 species andt herefore aimed at the isolation of carbene-stabilized arsenic monophosphide [(IMes)AsP(IDipp)] (4). Li...

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Section: Figurementioning

confidence: 99%

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confidence: 99%

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺

Doddi

Bockfeld

Zaretzke

et al. 2019

Chemistry A European J

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“…Unlike nitrenes and phosphinidenes, the triplet species of heavier group 15 elements are highly unstable and have only been investigated in the gas phase and in low‐temperature matrices. However, Bertrand et al recently reported on a stable singlet (phosphanyl)phosphinidene, and the corresponding (phosphanyl)arsinidene was observed as a transient species in solution . In addition, these reactive species were electronically stabilized by coordination to Lewis acidic metal centers as well as base‐coordination .…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures, and Bonding Analyses of Carbene‐Stabilized Stibinidenes

et al. 2019

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Reactions of two equivalents of LGa {L = HC[C(Me)NAr] 2 ; Ar = 2,6-iPr 2 -C 6 H 3 } with SbX 3 (X = Cl, Br) yield double-inserted products (LGaX) 2 SbX (X = Cl 1, Br 2), which were isolated at -40°C. Warming solutions of 1 and 2 to ambient temperature results in intramolecular elimination of LGaX 2 and formation of Ga-substituted stibinidenes L(X)GaSb as reaction intermediates, which were stabilized by coordination of strong σ-donating carbenes. Four carbene-stabilized stibinidenes Me CAAC-SbGa(X)L { Me CAAC = [H 2 C(CMe 2 ) 2 NAr]C, Ar = 2,6-iPr 2 -C 6 H 3 , X = Cl 3, Br 4} and IDipp-SbGa(X)L {IDipp = 1,3- [a] 1669 Scheme 3. Thermal treatment of isolated samples of 1 and reactions with one equivalent of LGa, yielding cyclotristibines, distibines, and gallastibenes.

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“…For example, Goicoechea and Hinz developed a method of generating the 2‐arsaethynolate anion, which was prepared from nonvolatile elemental arsenic . This method has been applied to obtain various unique arsenic‐containing molecules and complexes …”

Section: Introductionmentioning

confidence: 99%

“…[35] This method has been appliedt oo btain variousu nique arsenic-containing molecules and complexes. [35][36][37][38][39] In this context,n onvolatile intermediate transformation (NIT) methodsa re effective for promoting the advancement of organoarsenic chemistry.C yclooligoarsines are key synthetic intermediates for the developmento fp ractical AsÀCb ond formation reactions. It is worth noting that they can be safely prepared from nonvolatile inorganic arsenic compounds, and that the resulting materials have relatively high molecular weight and show negligible volatility under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

The Dawn of Functional Organoarsenic Chemistry

Imoto

Naka

2018

Chemistry A European J

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Organoarsenic chemistry was actively studied until the middle of 20th century. Although various properties of organoarsenic compounds have been computationally predicted, for example, frontier orbital levels, aromaticity, and inversion energies, serious concern to the danger of their synthetic processes has restricted experimental studies. Conventional synthetic routes require volatile and toxic arsenic precursors. Recently, nonvolatile intermediate transformation (NIT) methods have been developed to safely access functional organoarsenic compounds. Important intermediates in the NIT methods are cyclooligoarsines, which are prepared from nonvolatile inorganic precursors. In particular, the new approach has realized experimental studies on conjugated arsenic compounds: arsole derivatives. The elucidation of their intrinsic properties has triggered studies on functional organoarsenic chemistry. As a result, various kinds of arsenic-containing π-conjugated molecules and polymers have been reported for the last few years. In this minireview, progress of this recently invigorated field is overviewed.

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Intercepting a Transient Phosphino‐Arsinidene

Cited by 31 publications

References 52 publications

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺

Syntheses, Structures, and Bonding Analyses of Carbene‐Stabilized Stibinidenes

The Dawn of Functional Organoarsenic Chemistry

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Intercepting a Transient Phosphino‐Arsinidene

Cited by 31 publications

References 52 publications

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]+. and Dication [AsP]2+

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]+. and Dication [AsP]2+

Syntheses, Structures, and Bonding Analyses of Carbene‐Stabilized Stibinidenes

The Dawn of Functional Organoarsenic Chemistry

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Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺

Isolation of Carbene‐Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP]^+. and Dication [AsP]²⁺