RESUMEN
A synchrotron based vacuum ultraviolet absorption spectrum for γ-pyrone has been interpreted in terms of singlet excited electronic states using a variety of coupled cluster, configuration interaction, and density functional calculations. The extremely weak spectral onset at 3.557 eV shows eight vibrational peaks, which following previous analyses, are attributed to a forbidden 1A2 state. A contrasting broad peak with a maximum at 5.381 eV has a relatively high cross-section of 30 Mb; this arises from three overlapping states, where a 1A1 state dominates over progressively weaker 1B2 and 1B1 states. After fitting the second band to a polynomial Gaussian function and plotting the regular residuals over 20 vibrational peaks, we have had limited success in analyzing this fine structure. However, the small separation between these three states clearly shows that their vibrational satellites must overlap. Singlet valence and Rydberg state vibrational profiles were determined by configuration interaction using the CAM-B3LYP density functional. Vibrational analysis using both the Franck-Condon and Herzberg-Teller procedures showed that both procedures contributed to the profiles. Theoretical Rydberg states were evaluated by a highly focused CI procedure. The superposition of the lowest photoelectron spectral band on the vacuum ultraviolet spectrum near 6.4 eV shows that the 3s and 3p Rydberg states based on the 2B2 ionic state are present; those based on the other low-lying ionic state (X2B1) are destroyed by broadening; this is a dramatic extension of the broadening previously witnessed in our studies of halogenobenzenes.
RESUMEN
While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these are characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus.