AsS2Cl-an Arsenic(V) compound? Formation, stability and structure of gaseous AsSCl and AsS2Cl--a combined experimental and theoretical study

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 40; no. 25; pp. 6676 - 6683
• Main Authors: Milke, E, Köppe, R, Binnewies, M
• Format: Journal Article
• Language: English
• Published: England 01.01.2011
• Subjects: Bonding; Infrared radiation; Ionization; Mass spectrometry; Mathematical analysis; Quality control; Quantum chemistry; Stability
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c1dt10188a

By reaction of solid As(4)S(4) with gaseous Cl(2) at a temperature of 410 K gaseous AsSCl and AsS(2)Cl are formed. Unexpectedly in AsS(2)Cl the arsenic is not of formal oxidation state +V but +III: the molecular structure of AsS(2)Cl is arranged as a 1-chloro-dithia-arsirane and comprises an hitherto unknown AsS(2) three-membered ring. Thermodynamic data on AsSCl and AsS(2)Cl 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: Δ(f)H(0)(298)(AsSCl) = -5.2 kJ mol(-1) (MS), Δ(f)H(0)(298)(AsSCl) = 1.7 kJ mol(-1) (QC), S(0)(298)(AsSCl) = 296.9 J K(-1) mol(-1) (QC) and c(p)(0)(T)(AsSCl) = 55.77 + 3.97 × 10(-3)T- 4.38 × 10(5)T(-2)- 1.83 × 10(-6)T(2) and Δ(f)H(0)(298)(AsS(2)Cl) = -39.0 kJ mol(-1) (MS), Δ(f)H(0)(298)(AsS(2)Cl) = -20.2 kJ mol(-1) (QC), S(0)(298)(AsS(2)Cl) = 321.3 J K(-1) mol(-1) (QC) and c(p)(0)(T)(AsS(2)Cl) = 80.05 + 5.09 × 10(-3)T- 7.61 × 10(5)T(-2)- 2.35 × 10(-6)T(2) (298.15 K < T < 1000 K) (QC). The ionization energies are determined (IP(AsSCl) = 10.5, IP(AsS(2)Cl) = 10.2 eV). The IR spectrum of AsSCl is detected by means of matrix isolation spectroscopy. The estimated force constant f(As=S) = 4.47 mdyn·Å(-1) gives rise to an As=S double bond.