
%0 Journal Article
%A Chaston, SHH 
%A Livingstone, SE 
%A Lockyer, TN 
%A Pickles, VA 
%A Shannon, JS 
%T Thio derivatives of &#946;-diketones and their metal chelates. I. Some Monothio-&#946;-diketones and their nickel(II) chelates
%J Australian Journal of Chemistry
%D 1965/05/01
%V 18
%N 5
%P 673-689
%K 
%R https://doi.org/10.1071/CH9650673
%U https://www.publish.csiro.au/paper/CH9650673 
%X Monothio-&#946;-diketones of general formula RC(SH)=CHCOR? (R = Me, R* = Me, Ph, OEt; R = Ph, R' = Ph, OEt; R = &#945;-thienyl, R' = CF3; and 12 = R' = CMe,) have been prepared in order to study their metal complexes. Five of these thio derivatives are new and were prepared by treatment of a dilute solution of the corresponding &#946;-diketone in alcohol with hydrogen sulphide at low temperature. Mass spectrometric examination has established the structures of MeC(SH)=CHCOPh and RC(SH)=CHCOCF, (R = &#945;-thienyl).   The red compounds PhC(SH)=CHCOPh (VI) and MeC(SH)=CHCOPh (V) can be oxidized to yellow products. The structure of the yellow compound (XV) obtained from (VI) was established by mass and n.m.r. spectroscopy as the disulphide PhCOCH=C(Ph)SSC(Ph)=CHCOPh. The molecular ion of (XV) undergoes novel rearrangement reactions involving, inter alia, elimination of H2S to produce a thiophene ion.   The nickel chelates Ni(RCS=CHCOR')2 are brown, diamagnetic, and soluble in organic solvents. Unstable paramagnetic bis-pyridine adducts, derived from two of the nickel chelates, were isolated.   The infrared spectra of the monothio-&#946;-diketones and their nickel chelates are reported. The spectra of the monothio-&#946;-diketones show no SH band at c. 2570 cm-1 ; this indicates strong chelation of the thiol hydrogen between the sulphur and oxygen atoms. The monothio-&#946;-diketones display four characteristic bands which are assigned as follows : 1670-1590 cm-1, v(C--O) ; 1638-1530 cm-1, v(C=C) ; 1267-1190 cm-1, v(C=S) ; 837-805 cm-1, provisionally assigned as v(C=S) + &#948;(C-H). The nickel chelates exhibit five characteristic bands: 1590-1535 cm-1, V(C=C); 1542-1477 cm-1, v(C-0); 1261-1220 cm-1, v(C--S); 817-800 cm-1, provisionally assigned to v(C-S)+ &#948;(C-H); 499-451 cm-1, v(Ni-O). No band corresponding to v(Ni-S) was detected above 250 cm-1. However, the metal-sulphur stretching frequency was observed as a peak of medium intensity within the range 360-308 cm-1 in the spectra of bis(o-methylthiobenzenethiolo)-nickel(II) and the diethyl dithiophosphate complexes of nicke1(II), palladium(II), chromium(III), and cobalt(III). 
