The methods described in the literature for the synthesis of aliphatic thioketones are examined critically in the light of the authors' own work; new practical methods ofpreparation are reported, and characteristic properties a f thioketones are described.
The PPP procedure (neglect of the penetration integrals, constant parameters, idealized geometry, p model for the sulfur, and limited number of singly excited states in the configuration interaction) provides a satisfactory interpretation of the singlet-singlet absorptions of heterocyclic sulfur-containing compounds in the ultraviolet and visible spectral regions. The authors suggest the values US = 20 eV, PCS = 0.7Pc0, and 7 5 s = ycc as parameters for u-bivalent sulfur and employ the Mataga-Nishimoto relation for the two-center repulsion integrals. A reliable evaluation of the calculated charge distribution in the ground state would require additional experimental data.
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