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Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata-700 032, India E-mail : icac@iacs.res.in Manuscript received 18 September 2014, accepted 22 September 2014 The main contributions of Rây in the title area are presented and critically examined in the light of later developments. For mercury the cases examined include RSHg(NO2 ), [R3 S][HgI3 ] and HgCl2 (tu) (tu = thiourea). The RSHg(NO2 ) complex is probably a Hg-S-Hg bridged polymer incorporating nitrite ‘OO’ chelation. The system [R3 S][HgI3 ] is particularly noteworthy as [HgI3 – ] in the R = Me complex is a textbook example of transition metal tricoordination. In HgCl2 (tu), thiourea is bound in the usual thione form and not in the tautomeric thiol form which was invoked by Rây. He pioneered gold(III)-thioether chemistry through the first-ever synthesis and characterization of the family [Au(R2 S)Cl3 ]. His suggestion that [Au(Bz2 S)Cl2 ] is actually a ‘molecular compound’ of mono- and tri-valent species was later proven to be essentially correct but in a supramolecular lattice framework. |
