A Stable Heterocyclic Amino(phosphanylidene‐σ<sup>4</sup>‐phosphorane) Germylene

Rio, Natalia Del; Baceiredo, Antoine; Saffon‐Merceron, Nathalie; Hashizume, Daisuke; Lutters, Dennis; Müller, Thomas; Kato, Tsuyoshi

doi:10.1002/ange.201511956

Cited by 53 publications

(4 citation statements)

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“… 5 ( ii ) Formation of constitutional isomers: due to its ambident reactivity, the [OCP] − anion may bind through the P or the O center. Highly oxophilic species, such as s- 3c , 6 or f-block elements, 7 favor the oxyphosphaalkyne isomer, while soft Lewis acidic elements, for example, the heavy group 14 elements (Ge, Sn, Pb), 4b , 8 and Ga 4c , 9 favor the phosphaketene isomer. Both O- and P-bound isomers are known for B 4a , 10 and Si, 4b illustrating the ambident nature of the [OCP] − anion.…”

Section: Introductionmentioning

confidence: 99%

“…Within the realm of main-group elements, the reactivity of Na[OCP] has been established for group 2, 6a , 6b group 13, 4c , 9 , 10 group 14, 4b , 4e , 8 , 14 and group 15. 4e , 15 For the lattermost, these examples are limited to phosphorus and arscenic, with no current reports describing reactions of Na[OCP] with the heavier pnictogens (Sb and Bi).…”

Section: Introductionmentioning

confidence: 99%

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Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]

et al. 2021

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The synthesis and thermal redox chemistry of the first antimony (Sb)– and bismuth (Bi)–phosphaketene adducts are described. When diphenylpnictogen chloride [Ph 2 PnCl (Pn = Sb or Bi)] is reacted with sodium 2-phosphaethynolate [Na[OCP]·(dioxane) x ], tetraphenyldipnictogen (Ph 2 Pn–PnPh 2 ) compounds are produced, and an insoluble precipitate forms from solution. In contrast, when the N -heterocyclic carbene adduct (NHC)–PnPh 2 Cl is combined with [Na[OCP]·(dioxane) x ], Sb– and Bi–phosphaketene complexes are isolated. Thus, NHC serves as an essential mediator for the reaction. Immediately after the formation of an intermediary pnictogen–phosphaketene NHC adduct [NHC–PnPh 2 (PCO)], the NHC ligand transfers from the Pn center to the phosphaketene carbon atom, forming NHC–C(O)P-PnPh 2 [Pn = Sb ( 3 ) or Bi ( 4 )]. In the solid state, 3 and 4 are dimeric with short intermolecular Pn–Pn interactions. When compounds 3 and 4 are heated in THF at 90 and 70 °C, respectively, the pnictogen center Pn III is thermally reduced to Pn II to form tetraphenyldipnictines (Ph 2 Pn–PnPh 2 ) and an unusual bis -carbene-supported OCP salt, [(NHC) 2 OCP][OCP] ( 5 ). The formation of compound 5 and Ph 2 Pn–PnPh 2 from 3 or 4 is unique in comparison to the known thermal reactivity for group 14 carbene–phosphaketene complexes, further highlighting the diverse reactivity of [OCP] − with main-group elements. All new compounds have been fully characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy ( 1 H, 13 C, and 31 P), infrared spectroscopy, and elemental analysis ( 1 , 2 , and 5 ). The electronic structure of 5 and the mechanism of formation were investigated using density functional theory (DFT).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]

et al. 2021

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“…Protonation of PCO − in the presence of amine nucleophiles yielded phosphinecarboxamides ( B ) in a reaction analogous to Wöhler's historic synthesis of urea . Metathesis reactions provide access to various coordination complexes of main‐group elements, actinides, and transition metals as well as phosphaketene compounds of the Group 14 and 15 elements (silyl to plumbyl, germylenyl, and phosphanyl, C ). Furthermore, cycloaddition reactions towards alkynes, ketenes, and carbodiimides have also been reported .…”

Section: Figurementioning

confidence: 99%

A Monoanionic Arsenide Source: Decarbonylation of the 2‐Arsaethynolate Anion upon Reaction with Bulky Stannylenes

Hinz

Goicoechea

2016

Angew Chem Int Ed

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We report fundamental studies on the reactivity of the 2‐arsaethynolate anion (AsCO−), a species that has only recently become synthetically accessible. The reaction of AsCO− with the bulky stannylene Ter2Sn (Ter=2,6‐bis[2,4,6‐trimethylphenyl]phenyl) is described, which leads to the unexpected formation of a [Ter3Sn2As2]− cluster compound. On the reaction pathway to this cluster, several intermediates were identified and characterized. After the initial association of AsCO− to Ter2Sn, decarbonylation occurs to give an anion featuring monocoordinate arsenic, [Ter2SnAs]−. Both species are not stable under ambient conditions, and [Ter2SnAs]− rearranges to form [TerSnAsTer]−, an unprecedented anionic mixed Group 14/15 alkene analogue.

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“…More specifically, the former mode of compounds is largely the purview setting of s block's Ca [ 27 ] and Mg [ 28 ] elements as well as rare‐earth metal Sc, [ 29 ] Yb, [ 30 ] Sm, [ 30 ] etc . By contrast, d‐block's (Re, [ 31 ] Co, [ 32 ] Ir, [ 32 ] Au [ 32 ] ) and p block's (C, [ 26,33 ] P, [ 34‐39 ] Ge, [ 40‐45 ] Sn [ 36,40,45‐48 ] ) elements are favorable to form the latter pattern, although three unexpected examples have been structurally authenticated, which is not subject to the above rules. For example, Ga and Al of the same main group elements have significant differences in coordination modes with the 2‐phosphaethynolate anion.…”

Section: Introductionmentioning

confidence: 99%

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Liu

et al. 2021

Chin. J. Chem.

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Uranium | Thorium | Tripodal ligand |Computational chemistry | Electronic structureThe issue of covalence of actinide complexes remains controversial to date. The introduction of 2-phosphaethynolate anion into actinide complexes is expected to investigate the reaction mode and the bonding property. Herein, we describe the functionalization of An(Tren TIPS )Cl (1: An = U; 2: An = Th) precursors with NaOCP(dioxane) 2.5 through salt-elimination method leading to the formation of the corresponding uranium and thorium phosphaethynolate species: [U(Tren TIPS )(OCP)] ( 3) and [Th(Tren TIPS )(OCP)] (4). These two complexes were fully characterized by nuclear magnetic resonance (NMR), FT-IR spectrum, UV-vis-NIR spectroscopies as well as X-ray crystal diffraction. Computational analyses of the two complexes reveal that the U-O bond has a more covalent bond property than the Th-O bond due to more 5f orbital contribution for U.

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A Stable Heterocyclic Amino(phosphanylidene‐σ⁴‐phosphorane) Germylene

Cited by 53 publications

References 72 publications

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]

A Monoanionic Arsenide Source: Decarbonylation of the 2‐Arsaethynolate Anion upon Reaction with Bulky Stannylenes

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

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A Stable Heterocyclic Amino(phosphanylidene‐σ4‐phosphorane) Germylene

Cited by 53 publications

References 72 publications

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)2OCP][OCP]

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)2OCP][OCP]

A Monoanionic Arsenide Source: Decarbonylation of the 2‐Arsaethynolate Anion upon Reaction with Bulky Stannylenes

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

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A Stable Heterocyclic Amino(phosphanylidene‐σ⁴‐phosphorane) Germylene

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]

Indirect Access to Carbene Adducts of Bismuth- and Antimony-Substituted Phosphaketene and Their Unusual Thermal Transformation to Dipnictines and [(NHC)₂OCP][OCP]