Treatment of trivalent CpCoI(RF)L (1a-d) with AgF afforded fluoride complexes CpCoF(RF)L, 2a-d, in high yield ( RF = CF3, C2F5; L = PPh3, PPh2Me). The origin of the extreme 19F NMR chemical shifts for these Co fluorides (-716 to -759 ppm) was ascertained using computational methods. Complex 2c (RF = CF3, L = PPh2Me) serves as a catalyst for the addition of AgF to p-toluoyl chloride at room temperature. Reactions of 1c with Me3SiRF afforded the bis(fluoroalkyl) complexes CpCo(CF3)(RF)L, 3a,b. Selective fluoride abstraction from 3b using Me3SiOTf generates a cationic, electrophilic d6 fluorocarbene complex [CpCo=CF2(C2F5)L]+(OTf)- that undergoes fluoroalkyl transfer to yield the perfluoropropyl product, CpCo(C3F7)(OTf)L.

CpCo(III) fluoride and fluoroalkyl complexes: Selective C-F bond abstraction, C-C bond formation and catalyzed fluorination of acyl chlorides

251st National Meeting (2016)

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