Reactive EC(p‐p)π‐systems 53 [1]: Reactivity studies on perfluoro‐2‐arsapropene: [2+2]‐cycloaddition reactions and quantum chemical calculations

Albers, Thomas; Grobe, J.; Van, Duc Le; Maulitz, Andreas H.; Würthwein, Ernst‐Ulrich

doi:10.1002/hc.20118

Cited by 6 publications

(3 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The theoretical value of the C-C bond length in CCAs, r C-C = 1.2933 Å, calculated with density functional methods at the B3LYP/aug-cc-pVTZ level, 18 is in reasonable agreement, as well as r C-As = 1.7341 Å, determined from the laser-induced fluorescence ͑LIF͒ experiments of Wei et al 18 Table V also summarizes the C-As and C-C bond lengths of other relevant molecules. 15,17,18,20,[25][26][27][28][29] The ethylene C-C bond length of 1.339 Å is representative for a C v C double bond, while the acetylene C-C bond length, 1.202 Å, is typical of a C w C triple bond. Our experimental C-C bond distance of 1.287 Å for CCAs falls almost midway between the double and triple bond values.…”

Section: Discussionmentioning

confidence: 99%

“…For example, calculations on numerous arseniccontaining organic species have been carried out at various levels of theory to achieve an understanding of As-C bonding, and RAsv CF 2 -type molecules have been synthesized and their reactivity experimentally investigated. [14][15][16][17] Very recently, a novel arsenic-containing molecule has been produced in the gas phase and studied using electronic spectroscopy: arsenic dicarbide ͑CCAs͒, the smallest Asdoped carbon cluster. The 2 ⌬ r − X 2 ⌸ r band system of this free radical was investigated by Wei et al, 18 who were able to establish estimates of rotational constants for both the 12 C and 13 C isotopologues in the ⍀ = 1 2 ladder of the ground electronic state, X 2 ⌸ r .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

Sun

Clouthier

Ziurys

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

The pure rotational spectrum of the CCAs radical in its ground electronic and spin state, X (2)Pi(12), has been measured using Fourier transform microwave techniques in the frequency range of 12-40 GHz. This species was created in a supersonic expansion from a reaction mixture of AsCl(3) and C(2)H(2) or CH(4) diluted in high pressure argon, using a pulsed nozzle containing a dc discharge source. Three rotational transitions were measured for the main isotopologue, (12)C(12)CAs, in the Omega=12 ladder; both lambda-doubling and arsenic (I=32) hyperfine interactions were observed in these spectra. In addition, two to four rotational transitions were recorded for the (13)C(13)CAs, (13)C(12)CAs, and (12)C(13)CAs species. In these three isotopologues, hyperfine splittings were also resolved arising from the (13)C nuclei (I=12), creating complex spectral patterns. The CCAs spectra were analyzed with a case (a) Hamiltonian, and effective rotational, lambda-doubling, and arsenic and carbon-13 hyperfine constants were determined for the Omega=12 ladder. From the effective rotational constants of the four isotopologues, an r(m) ((1)) structure has been derived with r(C-C)=1.287 A and r(C-As)=1.745 A. These bond lengths indicate that the predominant structure for arsenic dicarbide is C=C=As, with some contributing C[Triple Bond]C and C[Triple Bond]As triple bond characters. The hyperfine constants established in this work indicate that about 23 of the unpaired electron density lies on the arsenic atom, with the remaining percentage on the terminal carbon. The value of the arsenic quadrupole coupling constant (eqQ=-202 MHz) suggests that the As-C bond has a mixture of covalent and ionic characters, consistent with theoretical predictions that both pi backbonding and electron transfer play a role in creating a linear, as opposed to a cyclic, structure for certain heteroatom dicarbides.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

Sun

Clouthier

Ziurys

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…The two simplest multiples bonded carbon-arsenic systems H 2 C@AsH [1][2][3][4][5][6][7][8][9][10][11] and HCAs [8][9][10][12][13][14][15] have been only very recently synthesized and characterized by Mass Spectrometry and UV-Photoelectron Spectroscopy. Also, their electronic structural properties have been investigated from a theoretical point of view thanks to the ionization energies computation by using several approaches.…”

Section: Introductionmentioning

confidence: 99%

The importance of anharmonicity in predicting the IR spectra of low coordinated organoarsenic compounds

Marchal¹,

Bégué²,

Chrostowska³

et al. 2010

Chemical Physics Letters

View full text Add to dashboard Cite

Cycloarsanes (AsCF₃)_n (n = 4, 5) – Precursors for the Highly Reactive Diarsene F₃CAs=AsCF₃

Grobe

Karst

Krebs

et al. 2006

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

Tetrakis(trifluoromethyl) cyclotetraarsane (F 3 CAs) 4 (2) was used to repeat the UV initiated [4ϩ2]-cycloaddition reaction of the diarsene F 3 CAsϭAsCF 3 (1) with cyclohexa-1,3-diene (CHD) and to isolate single crystals of the cycloadduct 4 for a X-ray diffraction analysis. 4 crystallizes in the space group P1 and contains the diarsene group in its E-configuration. 2 was also applied for [2ϩ2]-cycloaddition reactions of 1 with tBuCϵP and MeCϵC-N i Pr 2 , but in contrast to positive results with (F 3 CP) 4 the products were too labile for isolation. However, 2 was successfully used at room temperature as precursor for coordinating 1 as π-donor ligand to the Pd(PPh 3 ) 2 complex fragment yielding η 2 -bis(trifluoromethyl)diarsene-bis(triphenylphosphane)-palladium(0) 5, which was characterized by X-ray diffraction of single crystals and by spectroscopic investigations (NMR, IR, MS). Attempts to prove 599 the existence of the diarsene 1, generated by different methods, by spectroscopic studies very probably failed due to its extreme reactivity, not allowing the necessary concentrations for detection. Quantum chemical calculations of the stability of 1 with respect to dimerization, the stability of the [2ϩ2]-cycloadduct with 1-di(isopropyl)aminopropyne and the energy difference between 4 and the 2,3-dimethyl-1,3-butadiene cycloadduct of 1 were performed to understand the considerable differences between 1 and the related diphosphene F 3 CPϭPCF 3 .

show abstract

Reactive EC(p‐p)π‐systems 53 [1]: Reactivity studies on perfluoro‐2‐arsapropene: [2+2]‐cycloaddition reactions and quantum chemical calculations

Abstract: ABSTRACT:The extremely labile

Cited by 6 publications

References 41 publications

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

The importance of anharmonicity in predicting the IR spectra of low coordinated organoarsenic compounds

Cycloarsanes (AsCF₃)_n (n = 4, 5) – Precursors for the Highly Reactive Diarsene F₃CAs=AsCF₃

Contact Info

Product

Resources

About

Reactive EC(p‐p)π‐systems 53 [1]: Reactivity studies on perfluoro‐2‐arsapropene: [2+2]‐cycloaddition reactions and quantum chemical calculations

Abstract: ABSTRACT:The extremely labile

Cited by 6 publications

References 41 publications

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

The Fourier transform microwave spectrum of the arsenic dicarbide radical (CCAs: X̃Π1∕22) and its C13 isotopologues

The importance of anharmonicity in predicting the IR spectra of low coordinated organoarsenic compounds

Cycloarsanes (AsCF3)n (n = 4, 5) – Precursors for the Highly Reactive Diarsene F3CAs=AsCF3

Contact Info

Product

Resources

About

Cycloarsanes (AsCF₃)_n (n = 4, 5) – Precursors for the Highly Reactive Diarsene F₃CAs=AsCF₃