Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Abstract

The reaction of PF with [(Cy P) Pt] gave the PF complex trans-[(Cy P) PtF(PF )][PF ], which was characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy, and elemental analysis. To the best of our knowledge, this reaction is the first example of the oxidative addition of a P-F bond to a transition metal and is a rare example of an activation of a main-group-element-fluorine bond by a metal. Relativistic DFT calculations showed that the formation of the Lewis pair [(Cy P) Pt→PF ], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans-[(Cy P) PtF(PF )] was furnished by a two-step mechanism involving, successively, a second and a third PF molecule.

Synthesis and Reactivity of Iridium(I) Fluorido Complexes: Oxidative Addition of SF4 at trans‐[Ir(F)(CO)(PEt3)2]

“…All hydrogen atoms are omitted for clarity. Selected bond lengths /Å and angles /°with estimated standard deviations in parentheses: 9: Ir1-F1 1.965(5), Ir1-C1 1.838 (11), Ir1-P1 2.3266(4), O1-C1 1.156 (11); F1-Ir1-P1 88.37(2), F1-Ir1-C1 178.33(5), Ir1-C1-O1 178.99 (11); 10: Ir2-F2 1.9846 (19), Ir2-C2 1.800(3), Ir2-P3 2.3810(9), Ir2-P4 2.3901 (8), O2-C2 1.174(4), P3-Ir2-P4 172.98 3, P4-Ir2-F2 85.17(6), P4-Ir2-C2 93.96 (10), F2-Ir2-C2 169.88 (13), Ir2-C2-O2 176.4 (3).…”

“…[1a], [1b], The preparation of transition metal fluorido complexes can be achieved either by treatment of metal fluorides with ligand precursors, by fluorination of suitable complexes or by the activation of element–fluorine bonds. [1a], [1b], [2l], Apart from C–F bond activation reactions,[2e], [2f], [2h], [2l], this also includes reactions with SF 4 or SF 6 . SF 4 is typically used as a tool for the fluorination of oxygen containing compounds, but has so far received only little attention in transition metal chemistry.…”

“…, C 6 D 6 , 298 K): δ = 1.81 (mq,3 J H,H = 7.5 Hz, 12 H, PCH 2 CH 3 ), 1.06 ppm (mt, 3 J H,H = 7.5 Hz, 18 H, PCH 2 CH 3 ); 3 J H,Hand 3 J H,P -coupling constants were determined from a 1 H{ 31 P} NMR spectrum 19. F NMR (282.4 MHz, C 6 D 6 , 298 K): δ = -264.8 ppm (t, 2 J F,P = 33 Hz).…”

Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation, Fluoride Migration, and Hydrogen Bonding

“…presented the formation of a trifluorophosphane platinum( ii ) fluorido complex by P−F bond activation of PF 5 . [6k] …”

Theoretical Study on Si−Cl Bond Activation in Pd‐Catalyzed Cross‐Coupling of Chlorosilanes with Organoaluminum

“…In the trans-oxidative addition pathway, the apical SiÀ Cl bond in the σ-acceptor (Z-type) chloro-silane ligand is eliminated to directly afford the trans-chloro-silyl complex (Figure 1a). This peculiar oxidative addition has been proposed for polar and strong BÀ X (X=F [16] and Br [17] ), PÀ F, [18] and InÀ X (X=Cl, Br, and I) [19] bond activation using 14-electron Pt{P(t-Bu 3 )} 2 complex. In addition, S N 2-type [12c] and concerted cisoxidative addition [12b] have been proposed in earlier theoretical studies for SiÀ Cl bonds (Figure 1b and 1c).…”