Synthesis and Reactivity of the Fluoro Complex <i>trans</i>-[Pd(F)(4-C<sub>5</sub>NF<sub>4</sub>)(<sup><i>i</i></sup>Pr<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>OCH<sub>3</sub>)<sub>2</sub>]: C–F Bond Formation and Catalytic C–F Bond Activation Reactions
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The reaction of [Pd(Me)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine iPr2PCH2CH2OCH3 resulted in the formation of the palladium(0) complex [Pd(iPr2PCH2CH2OCH3)2] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C–F activation product trans-[Pd(F)(4-C5NF4)(iPr2PCH2CH2OCH3)2] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)(iPr2PCH2CH2OCH3)2] (4) and trans-[Pd(Br)(4-C5NF4)(iPr2PCH2CH2OCH3)2] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)(iPr2PCH2CH2OCH3)2] (6) and trans-[Pd(H)(4-C5NF4)(iPr2PCH2CH2OCH3)2] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)2, TolB(OH)2, or HBpin when 5 mol % of 2 is employed as catalyst.
