The oxidative addition of HF at trans‐[Ir(ArF)(η2‐C2H4)(PiPr3)2] (1a: ArF = 4‐C5NF4; 1b: ArF = 2‐C6H3F2) affords the fluorido complexes trans‐[Ir(ArF)(F)(H)(PiPr3)2] (2a: ArF = 4‐C5NF4; 2b: ArF = 2‐C6H3F2). The hydrido fluorido complex 2a is also accessible by means of the reaction of the hydroxido complex trans‐[Ir(4‐C5NF4)(H)(OH)(PiPr3)2] (3a) with Et3N·3HF. Both compounds 2a and 2b react with CO to give the carbonyl complexes trans‐[Ir(4‐C5NF4)(F)(H)(CO)(PiPr3)2] (4a: ArF = 4‐C5NF4; 4b: ArF = 2‐C6H3F2). In the presence of traces of water, a slow reaction of 2a with CO2 yields the hydrogencarbonato complex trans‐[Ir(4‐C5NF4)(H)(κ2‐(O,O)‐O2COH)(PiPr3)2] (5a). Upon using 2a or 2b as fluorinating agent, Ph3SiH could be converted into Ph3SiF and CH3C(O)Cl into CH3C(O)F.

The reaction of [Pd(Me) 2 (tmeda)] (tmeda = N,N,N′,N′-tetramethylethylendiamine) with the phosphine i Pr 2 PCH 2 CH 2 OCH 3 resulted in the formation of the palladium(0) complex [Pd( i Pr 2 PCH 2 CH 2 OCH 3 ) 2 ] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C−F activation product trans-[Pd(F)(4-C 5 NF 4 )-( i Pr 2 PCH 2 CH 2 OCH 3 ) 2 ] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C 5 NF 4 )( i Pr 2 PCH 2 CH 2 OCH 3 ) 2 ] (4) and trans-[Pd(Br)(4-C 5 NF 4 )( i Pr 2 PCH 2 CH 2 OCH 3 ) 2 ] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me 3 SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C 5 NF 4 )( i Pr 2 PCH 2 CH 2 OCH 3 ) 2 ] (6) and trans-[Pd(H)(4-C 5 NF 4 )-( i Pr 2 PCH 2 CH 2 OCH 3 ) 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.

Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF led to a variety of fluorido and fluorovinyl complexes.

A reaction of trans-[Ir(4-C(5)NF(4))(η(2)-C(2)H(4))(PiPr(3))(2)] (1) with an excess of water in THF at room temperature affords the hydrido hydroxo complex trans-[Ir(4-C(5)NF(4))(H)(OH)(PiPr(3))(2)] (2). Treatment of 2 with CO furnishes trans-[Ir(4-C(5)NF(4))(H)(OH)(CO)(PiPr(3))(2)] (3). Reductive elimination of water from 3 leads to the formation of the iridium(I) carbonyl complex trans-[Ir(4-C(5)NF(4))(CO)(PiPr(3))(2)] (4). The insertion of CO(2) into the Ir-O bond of 2 forms the hydrido hydrogencarbonato complex trans-[Ir(4-C(5)NF(4))(H)(κ(2)-(O,O)-O(2)COH)(PiPr(3))(2)] (5). Treatment of 2 with NH(3) in C(6)D(6) yields trans-[Ir(4-C(5)NF(4))(H)(OH)(NH(3))(PiPr(3))(2)] (6). Storage of the reaction mixture at room temperature reveals the formation of the N-H activation product [Ir(4-C(5)NF(4))(H)(μ-NH(2))(NH(3))(PiPr(3))](2) (7).

The complex cis-trans-[Ir(