Insertion of CS₂ into Iridium–Fluorine Bonds

Abstract

CS2 funkt dazwischen: C‐F‐Bindungsbildung führt in den Reaktionen der Fluoridokomplexe trans‐[Ir(ArF)(F)(H)(PiPr3)2] (ArF=4‐C5NF4; siehe Schema) mit CS2 zu Fluordithiocarbonato‐Spezies trans‐[Ir(ArF)(H)(κ2‐(S,S)‐S2CF)(PiPr3)2]. DFT‐Rechnungen sprechen für einen ungewöhnlichen, konzertierten metatheseartigen Mechanismus des C‐F‐Bindungsbildungsschritts, in dem CS2 in die Ir‐F‐Bindung inseriert.

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

“…A comparable small P,P coupling constant for metal-bound phosphorus atoms in the cisposition was found for other platinum(II) complexes. 24,45,[77][78][79][80][81][82][83][84][85][86] The reactivity of [Pt(xantphos)(η 2 -PhCuCPh)] (2), which bears the xantphos ligand that exhibits a larger bite angle, was also investigated. Both P,F coupling constants are also observed in the 19 F{ 1 H} NMR spectrum as a doublet of doublets with 195 Pt satellites at δ −240 ppm ( 1 J Pt,F = 197 Hz).…”

“…The chemical shift as well as the coupling constants are characteristic of a transition metal bound fluorido ligand. 24,45,[77][78][79][80][81][82][83][84][85][86] The reactivity of [Pt(xantphos)(η 2 -PhCuCPh)] (2), which bears the xantphos ligand that exhibits a larger bite angle, was also investigated. 87,88 Treatment of 2 with NFSI at room temperature led to a product mixture which consisted of complex Pt satellites.…”

“…Insertion reactions of unsaturated organic molecules into metalfluorine bonds, which would resemble an alternative reaction pathway, are extremely rare. 50,54,82 However, the characterization of a complex bearing the fluorinated ligand after an attack of an electrophilic fluorinating agent at a metal coordinated substrate is also unique, but represents an important key step for a putative catalytic cycle. 69,70 Note in addition that in none of the conversions a fluoroamination product PhFCvCN(SO 2 Ph) 2 Ph was observed.…”

Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)3

“…Such a reversion of a C–F activation step at a highly fluorinated aromatic ligand is unique and has never been considered before. 3 , 7 …”