THERMAL AND PHOTOLYTIC SUBSTITUTION OF DITECHNETIUM AND DIRHENIUM DECACARBONYL WITH TRIFLUOROPHOSPHINE

The substitution reaction of Tc2(CO)10 and Re2(CO)10 with PF3 has been studied under both thermal and photolytic conditions. Complete substitution was not observed for either system. Substitution of up to nine of the ten carbonyls by PF3 results in the formation of at least 33 different species in the rhenium system. In the technetium system, substitution of up to eight of the carbonyls results in the formation of at least 24 different species. The disubstituted products 1,1ʹ-M2(CO)8(PF3)2 and 2,2ʹ-M2(CO)8(PF3)2 (M = Re or Tc) are readily formed, but formation of 1,2ʹ-Re2(CO)8(PF3)2 was not observed. © 1990, American Chemical Society. All rights reserved.