Cooperative effects of different transition metals attract considerable interests in relation to multimetallic catalyses. We have reported series of heterodinuclear organoplatinum and �palladium complexes L2RM-M'L'm, including various enhanced reactivities. [1]. Selectivity control in ring-opening reactions of thiranes and thietanes by heterodinuclear organoplatinum-manganese complexes is described. Metathesis of PtMeX(dppe) with Na[Mn(CO)5] gave non-bridged heterodinu7clear complex (dppe)MePt-Mn(CO)5 (1 ) whereas treatment of the neopentyl analogue cause intramolecular CO insertion to give its isomer, (dppe)Pt(COCH2CMe3-k2C,O)Mn(CO)4 (2 ). Addition of CO to 2  gave a corresponding non-bridged complex (dppe)(COCH2CMe3)Pt-Mn(CO)5 (3 ). Non-bridged complexes 2  and 3  reacted with cis- and trans-2-butene sulfides to give corresponding platinum complexes coordinated by thiamanganacyclic ketone with inversion stereochemistry by an SN2 type mechanism. Further heating liberated trans- and cis-2-butenes with retention stereochemistry. In sharp contrast, the bridged complex 2  caused direct desulfurization of cis- and trans-2-butene sulfide with retention of configuration, giving cis- and trans-2-butenes, respectively, probably due to strong Pt-Mn bond by acyl bridge forcing the concertd direct desulfurizarion pathway.Reference [1] S. Komiya, Coord. Chem. Rev., 2012 , 256, 556

Selectivity control in C-S bond cleavage reaction of thiiranes and thietanes by bridged and non-bridged heterodinuclear organoplatinum-manganese complexes

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.