The Formation of the Neutral Isomers NCCCCO and CCC(O)CN in the Gas Phase from Ionic Precursors:  a Joint Experimental and Theoretical Study

Dua, Suresh; Peppe, Salvatore; Bowie, John H.

doi:10.1021/jp020524g

Cited by 8 publications

(6 citation statements)

References 43 publications

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“… , Cyanoketene itself has been prepared only in matrix isolation experiments and discussed as a potential interstellar molecule, important due to its potential role in prebiotic chemistry. − Thus, the isolation of the anion represents an important discovery since it allows not only its use as synthetic building block but also reactivity studies with other interstellar molecules. In the solid state structure of [K([2,2,2]cryptand)] + complex of 31 , the cyanoketene anion shows a bent geometry around the central carbon atom with a large C2–C1–C3 angle of 166.4(2)°, contradicting earlier calculations that reported the anion to be linear ( 31’ or 31″ ). − This is further evidenced by the IR spectrum of the anion, which displays three distinct signals in the region corresponding to the primary asymmetric and symmetric stretching vibrations.…”

Section: Ligand Exchange At Metalated Speciesmentioning

confidence: 77%

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

Krischer,

Gessner

2024

JACS Au

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How different is carbon compared to other elements in the periodic table? Can carbon compounds be regarded as coordination complexes with carbon as the central element undergoing a facile exchange of its ligands? Although carbon clearly plays a special role among the elements of the periodic table, recent studies have drawn parallels between the bonding situation and the reactivity of carbon compounds to transition metal complexes. This Perspective summarizes recent reports about ylidic and zwitterionic compounds that were shown to exhibit ambiguous bonding situations that can be interpreted as donor–acceptor interactions similar to the bond between a metal and a neutral ligand. Based on this conception, ligand exchange reactions prototypical of transition metal complexes were realized at carbon atoms, enabling new synthetic strategies for the synthesis of reactive species and building blocks. In particular, the exchange of N2, CO, and phosphine ligands led to the development of a mild method for accessing new compounds and reagents with unusual properties, such as vinylidene ketenes or stable ketenyl anions, that open up a diverse but still poorly explored follow-up chemistry.

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Section: Ligand Exchange At Metalated Speciesmentioning

confidence: 77%

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

Krischer,

Gessner

2024

JACS Au

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“…The cyanoketenyl anion [NCCCO]‐ 2 has likewise been proposed to be an interstellar species, [9] but until now little is known about its spectroscopic properties required for its detection. Unlike its isoelectronic analog, carbon suboxide (C 3 O 2 ), anion 2 has not yet been isolated in bulk phase, but was prepared in gas phase and detected by mass spectrometry [10]…”

Section: Figurementioning

confidence: 99%

“…now [7] but has been subjected to matrix isolation, gas phase and computational studies, addressing possible isomers and routes for its formation such as through irradiation of ozone in the presence of cyanoacetylene on a water ice surface or the thermolysis of cyanoacyl chloride (Figure 1b). [8] The cyanoketenyl anion [NCCCO]-2 has likewise been proposed to be an interstellar species, [9] but until now little is known about its spectroscopic properties required for its detection. Unlike its isoelectronic analog, carbon suboxide (C 3 O 2 ), anion 2 has not yet been isolated in bulk phase, but was prepared in gas phase and detected by mass spectrometry.…”

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confidence: 99%

The Cyanoketenyl Anion [NC₃O]⁻

Krischer,

Swamy,

Feichtner

et al. 2024

Angewandte Chemie

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Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for more complex molecules but tend to isomerize or cyclize and therefore are difficult to isolate. Using a mild ligand exchange reaction at the carbon in metalated ylides, we have now succeeded in the synthesis and gram‐scale isolation of the elusive cyanoketenyl anion [NC3O]‐. Despite its assumed cumulene‐like structure and the delocalization of the negative charge across the whole 5‐atom molecule, it features a bent geometry with a nucleophilic central carbon atom. Computational studies reveal an ambiguous bonding situation in the anion, which can be illustrated only by a combination of different resonance structures. Nonetheless, the anion features remarkable stability, thus allowing the storage of its potassium‐crown ether salt and its application as a highly functional synthetic building block. The cyanoketenyl anion readily reacts with a series of small molecules to form more complex organic compounds, including industrially valuable compounds such as cyanoacetate. This work demonstrated that reactive species can be generated by novel synthesis methods and open up atom‐economic pathways to complex compounds from small abundant molecules.

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“…A joint experimental and theoretical study shows that doublet CCC(CO)CN rearranges to OCCCCN via a three-membered ring intermediate as shown in Seq. (11) of Scheme 9, and that the energized species OCCCCN so formed, may decompose to CCCN and CO: a process which requires only 38.5 kcal mol À1 (Dua & Bowie, 2002b). 2.…”

Section: E Miscellaneous Processesmentioning

confidence: 99%

Studies of cyclization reactions of linear cumulenes and heterocumulenes using the neutralization–reionization procedure and/or ab initio calculations

Wang

Bowie

2011

Mass Spectrometry Reviews

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A number of linear cumulenes and heterocumulenes have been made by charge stripping of anions of known bond connectivity in the source of a mass spectrometer. Some of these reactive molecules have been identified in interstellar molecular clouds. The structures of these neutrals may be investigated by reionization to a decomposing positive ion [the neutralization-reionization technique ((-)NR(+))], and/or by ab initio calculations. Energized linear cumulenes and heterocumulenes may undergo cyclization to form stable cyclic isomers. To cite a selection of the examples described in this review: (i) four-atom systems CCCC and some heterocumulenes CCCX (X=B, N, Al, Si, P) involve the formation of stable four-membered ring rhombic (also called kite and fan) structures. One of the cyclic molecules, cyclo-C(3) Si, has been detected in interstellar molecular clouds, (ii) five-atom cumulene and heterocumulene systems are more complex. Linear CCCCC rearranges the carbon skeleton by forming a C substituted rhomboid system, CCCCO forms a three-membered cyclic isomer, while nitrogen containing five-atom cumulenes effect nitrile to isonitrile interconversion via three-centered cyclized intermediates, and (iii) CCCCCC and CCCCBO cyclize to give unique six-membered ring systems.

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The Formation of the Neutral Isomers NCCCCO and CCC(O)CN in the Gas Phase from Ionic Precursors: a Joint Experimental and Theoretical Study

Cited by 8 publications

References 43 publications

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

The Cyanoketenyl Anion [NC₃O]⁻

Studies of cyclization reactions of linear cumulenes and heterocumulenes using the neutralization–reionization procedure and/or ab initio calculations

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The Formation of the Neutral Isomers NCCCCO and CCC(O)CN in the Gas Phase from Ionic Precursors: a Joint Experimental and Theoretical Study

Cited by 8 publications

References 43 publications

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

The Cyanoketenyl Anion [NC3O]−

Studies of cyclization reactions of linear cumulenes and heterocumulenes using the neutralization–reionization procedure and/or ab initio calculations

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The Cyanoketenyl Anion [NC₃O]⁻