Issue 25, 2011

AsS2Cl—an Arsenic(v) Compound? Formation, Stability and Structure of gaseous AsSCl and AsS2Cl—a combined experimental and theoretical study

Abstract

By reaction of solid As4S4 with gaseous Cl2 at a temperature of 410 K gaseous AsSCl and AsS2Cl are formed. Unexpectedly in AsS2Cl the arsenic is not of formal oxidation state +V but +III: the molecular structure of AsS2Cl is arranged as a 1-chloro-dithia-arsirane and comprises an hitherto unknown AsS2 three-membered ring. Thermodynamic data on AsSCl and AsS2Cl are obtained by mass spectrometry (MS). The experimental data are extended and confirmed by ab initio quantum chemical calculations (QC). The following values are given: ΔfH0298(AsSCl) = −5.2 kJ mol−1 (MS), ΔfH0298(AsSCl) = 1.7 kJ mol−1 (QC), S0298(AsSCl) = 296.9 J K−1 mol−1 (QC) and cp0T(AsSCl) = 55.77 + 3.97 × 10−3T − 4.38 × 105T−2 − 1.83 × 10−6T2 and ΔfH0298(AsS2Cl) = −39.0 kJ mol−1 (MS), ΔfH0298(AsS2Cl) = −20.2 kJ mol−1 (QC), S0298(AsS2Cl) = 321.3 J K−1 mol−1 (QC) and cp0T(AsS2Cl) = 80.05 + 5.09 × 10−3T − 7.61 × 105T−2 − 2.35 × 10−6T2 (298.15 K < T < 1000 K) (QC). The ionization energies are determined (IP(AsSCl) = 10.5, IP(AsS2Cl) = 10.2 eV). The IR spectrum of AsSCl is detected by means of matrix isolation spectroscopy. The estimated force constant f(As[double bond, length as m-dash]S) = 4.47 mdyn·Å−1 gives rise to an As[double bond, length as m-dash]S double bond.

Graphical abstract: AsS2Cl—an Arsenic(v) Compound? Formation, Stability and Structure of gaseous AsSCl and AsS2Cl—a combined experimental and theoretical study

Article information

Article type
Paper
Submitted
02 Feb 2011
Accepted
07 Apr 2011
First published
31 May 2011

Dalton Trans., 2011,40, 6676-6683

AsS2Cl—an Arsenic(V) Compound? Formation, Stability and Structure of gaseous AsSCl and AsS2Cl—a combined experimental and theoretical study

E. Milke, R. Köppe and M. Binnewies, Dalton Trans., 2011, 40, 6676 DOI: 10.1039/C1DT10188A

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