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Extra info for Progress in Inorganic Chemistry: Inorganic Reaction Mechanisms: Part II, Volume 17
Emission from the excited ligand field triplet (TI) of cis-Rh(phen),Xz + has been observed (101a) ;for the second row rhodium(II1) ion these d states are at lower energy than the CT states. ] Apparently, PtBr,2 - undergoes a simple photoaquation reaction (102) ; however, under flash photolysis conditions (22,103) or in the presence of added Br- ion (16) more complicated oxidation reduction mechanisms are detected. ) The flash photolysis (103) of PtBrs2- does not produce Br or Br2-, as in the case of Co(NH3),Br2+ or as expected from photoexchange studies (16), but instead yields a comparatively long lived transient species (ts z Is), 34 P.
98), &[PtCI,] solid powder at 77°K (-, right scale; ref. 105b). 100 80 - 2 60- . -" I h 'CT 3tig 3CT 'Tlq 2 W 40- 20 'Alp 0I Fig. 10. Schematic energy level diagram for a d6 metal complex in an octahedral field, showing the possible absorption, emission, and some of the radiationless (--) transitions. 36 EXCITED STATES OF METAL COMPLEXES 37 (94,108), Co(CN),,- and CO(CN),(SO,),~- (see Table IX). Both show d-d phosphorescence. The bulk of emission experiments has been conducted with the heavier metals ruthenium(II), osmium(lI), rhodium(IlI), and iridium(III), and most of this work has involved the phenanthrolene and dipyridine complexes.
FLETSCHAUER, A. W. ADAMSON, AND G . SARTORI which has maximum absorption between 400 and 450 nm (22). This species is believed to be Br,, formed according to reaction (24). The bromine formed behaves as a transient because of hydrolysis and oxidation reactions with [PtBr4,-]. PtBra2- hv_ [PtBr4,-] + Br, (24) An alternative possibility is that the long-lived transient is a Pt(II1) species like the one observed in the flash photolysis of PtC1e2- (169). Unlike PtC1e2-, however, there was no Br or Br2- observed in the flash of PtBre2(103).