The synthesis of the simplest heterocompounds bearing a multiple carbon-heteroatom bond is a permanent challenge since most of them are not kinetically stable and only the carbon-oxygen double bond (aldehydes and ketones) and carbon-nitrogen triple bond derivatives (nitriles) are kinetically stabilized. As part of our systematic investigation of the heavier group 15 element hetero-analogues of alkenes [1-3] and alkynes [1], our attention is focused on low-coordinate arsenic derivatives, particularly interesting by their physicochemical properties and especially for their photoelectron spectral data, which allow to determine the energy of the orbitals involved in the carbon-heteroatom bond. Limited information exists concerning the electronic structures of weakly hindered species, and most of what is available is derived from theoretical studies [4]. The aim of this work is to study the structural and electronic properties of these highly reactive - simplest arsaalkenes 1a-d formed by dehydrohalogenation of the corresponding α-chloroarsines 2a-d in vacuum gas solid reaction (VGSR) conditions. In order to estimate the effect of the methyl substitution on carbon-arsenic double bond, UV photoelectron spectroscopic characterization has been applied. Theoretical calculations (B3LYP/6-311G(d,p); OVGF/6-311G(d,p)) of the ionisation potentials for these molecules have been carried out to assist in the reliable assignment of the experimental data.

[1] V. Métail , A. Senio, L. Lassalle, J.-C. Guillemin, G. Pfister-Guillouzo, Organometallics 1995, 14, 10, 4732.

[2] A. Chrostowska, A. Dargelos, V. Lemierre, J.-M. Sotiropoulos, P. Guenot, J.-C. Guillemin, Angew. Chem. Int. Ed. 2004, 43, 873-875.

[3] A. Chrostowska, V. Lemierre, A. Dargelos, J.-M. Sotiropoulos, J.-C. Guillemin, Applied Organometallic Chemistry 2004, 18, 690-693.

[4] V. Lemierre, A. Chrostowska, A. Dargelos, H. Chermette, Journal of Physical Chemistry A 2005, 109, 8348-8355.

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1. Studies on Flash Vacuum Thermolysis of Thiones of Selected N-, O-, and S-heterocycles