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

Hinz, Alexander; Goicoechea, José M.

doi:10.1002/anie.201609309

Cited by 45 publications

(39 citation statements)

References 65 publications

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“…[51] Ther eactive stannyl pnictogenyls [Ter 2 Sn À X] À formed as initial products after loss of CO could nevertheless be isolated for the arseninidine derivative.Incase of X = P, only the head-to-head dimer,[ Ter 2 SnÀP=PÀSnTer 2 ] 2À , could be detected by NMR in low yield. These adducts are highly unstable and lose CO either thermally or under radiation with light.…”

Section: Reviewsmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Reviewsmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…[83,84] Dimerization of the E-form vinyl radical species produces cyclic diarsenic compounds, cis-DHDAs (32). Platinum,p alladium,g old, and copperc omplexes with cis-DHDA ligands (33)(34)(35)(36)(37)w ere synthesized (Scheme 18). [85][86][87][88][89][90][91][92] Notably,t he two arsenic atoms are fixed at as hort distance (ca.…”

Section: Poly(vinylenearsine)smentioning

confidence: 99%

“…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%

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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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“…Ther eport of several novel syntheses of the ion as the more stable sodium and potassium salts has rekindled interest in this reagent. [13] To date,c yanate analogues containing both heavier Group 15 and Group 16 elements are limited to the 2phosphaethynthiolate anion (PCS À )which can be synthesised by reaction of PCO À with CS 2 .Aswith PCO À ,this species was first isolated by Becker and Hübler, [14] and its chemistry has largely been limited to fundamental coordination chemistry studies and some gas-phase measurements. [9][10][11] Theh eavier arsenic-containing ion, AsCO À ,w as first isolated in 2016 by our research group, [12] and promises to be as imilarly versatile reagent in chemical synthesis,h aving already been employed for the synthesis of several novel molecules.…”

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A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

et al. 2018

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Ag eneral synthetic protocol for the synthesis of phosphorus-and arsenic-containing analogues of the thio-and seleno-cyanate anions is reported. This procedure allows for the isolation of three unprecedented species:t he phosphaethynselenolate,P CSe À (1), the arsaethynthiolate,A sCS À (2), and the arsaethynselenolate,A sCSe À (3), anions.T he structures,e lectronic properties,a nd spectroscopic signatures of these species are reported. Scheme 1. Synthesis of [Na(18-crown-6)(THF) 2 ][PnCCh]( where Pn = P, As; Ch = S, Se).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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

Cited by 45 publications

References 65 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

The Dawn of Functional Organoarsenic Chemistry

A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

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