Synthesis and Spectroscopic Characterization of Ethylidynearsine

Abstract

Ethynylarsine (2a) is synthesized by reaction of arsenic trichloride with ethynyltributylstannane followed by a chemoselective reduction of the formed ethynyldichloroarsine (la). The base-induced rearrangement of compound 2a on a solid base in VGSR conditions leads to ethylidynearsine (3a) characterized by 1 H and 13C NMR and by microwave spectroscopy. The rotational spectrum of 3a is recorded in the frequency range 90-470 GHz. Rotational and centrifugal distortion constants are determined and the quadrupole hyperfine structure is analyzed. The structure of CH~CIAS has been estimated from the rotational constants of eight different isotopic species and from ab initio calculations. Compound 3a exhibits a low stability at 0 OC in deuteriochloroform (~1 1 2 ca. 1 h) or in the gaseous phase at a pressure of 10 Pa (~1 / 2 ca. 30 min).

[(CF3)3BCP]− and [(CF3)3BCAs]−: Thermally Stable Phosphaethynyl and Arsaethynyl Complexes

“…In both spectra there are two resonance signals in an intensity ratio of 1:3, assigned to the CX À ligands and the CF 3 groups, respectively. The position and coupling pattern of the 13 [3][4][5][6][7] However, an unambiguous assignment is made pos- À1 to lower wavenumber in the (negatively charged) borate complex (Table 2). [4] There are no vibrational data available for arsaalkynes and hence n(CAs) in [(CF 3 ) 3 BCAs] À is the first example.…”

Acidity Trends in α,β‐Unsaturated Sulfur, Selenium, and Tellurium Derivatives: Comparison with C‐, Si‐, Ge‐, Sn‐, N‐, P‐, As‐, and Sb‐Containing Analogues

“…Even for arsenic or tin, it is only quite recently that the corresponding derivatives have been synthesized. [5][6][7][8] On the other hand, the high reactivity of other heterocomAbstract: The gas-phase acidity of CH 3 ÀCH 2 XH (X = S, Se, Te), CH 2 =CHXH (X = S, Se, Te) and PhXH (X = S, Se) compounds was measured by means of Fourier transform ion cyclotron resonance mass spectrometry. To analyze the role that unsaturation plays on the intrinsic acidity of these systems, a parallel theoretical study, in the framework of the G2 and the G2-(MP2) theories, was carried out for all ethyl, ethenyl (vinyl), ethynyl, and phenyl O-, S-, Se-, and Te-containing derivatives.…”

[(CF3)3BCP]− und [(CF3)3BCAs]− –thermisch stabile Phosphaethinyl‐ und Arsaethinyl‐Komplexe

“…Die C-As-Bindungslänge von 1.675(12) entspricht den Werten für Mes*CAs (1.657 (7) ) [26] und CH 3 CAs (1.661 (1) ). [13] Die Struktur von [PPh 4 ][(CF 3 ) 3 BCP] wurde analog verfeinert, ihre Qualität ist allerdings schlechter.…”

“…Außerdem wirkt vermutlich auch die Wechselwirkung des Aryl-p-Systems mit der C-As-Dreifachbindung stabilisierend. Das einzige weitere bekannte Arsaalkin, CH 3 CAs, [13] ist bei Raumtemperatur instabil. Die Stammverbindung HCAs wurde bisher nicht beschrieben, und auch tBuCAs konnte nicht synthetisiert werden.…”