Sensing of Aqueous Fluoride Anions by Cationic Stibine–Palladium Complexes

Abstract

Turn on the lantern! The stibine donor ligand of a cationic palladium complex acts as a Lewis acid and reacts with a fluoride anion to afford the corresponding fluorostiboranyl-palladium species (see scheme). Bindung of the fluoride anion to the antimony center induces a change in denticity of the triphosphine unit and leads to a bright-orange trigonal-bipyramidal d(8) lantern complex.

Neutral organoantimony(III) and organobismuth(III) ligands as acceptors in transition metal complexes – Role of substituents and co-ligands

“…respectively with [NBu4]F ( Figure 22). 46 Once again the halide, in this case fluoride, reacts with the Sb centre rather than the transition metal, forming a SbF bond. In the latter compound, this leads to a rearrangement of the geometry at Pd from square planar to trigonal bipyramidal, caused by coordination of the (previously uncoordinated) third phosphine moiety.…”

Hypervalent diorganoantimony(iii) fluorides via diorganoantimony(iii) cations – a general method of synthesis

“…7,8 This is, so far, the only R 2 SbF species investigated by single-crystal X-ray diffraction; its solid state structure consisting of innite chains of Ph 2 SbF units connected by strong intermolecular uorine bridges. 8 It should be noted here that organotin(IV) uorinating agents such as Me 3 14 Several other methods failed to produce the desired Ph 2 SbF derivative. 8 Thus, the reaction of Ph 2 SbCl with AgF in acetonitrile and AsF 3 afforded the organoantimony(V) species Ph 3 SbF 2 following a process of simultaneous oxidative uorination and redistribution of the phenyl groups.…”

“…28 While the resulting SbC 3 N rings are basically planar for the imine ligands in 5 and 6, the C 3 SbN rings in 7 and 8 are folded along the Sb/C methylene axis, with the N(sp 3 ) atom lying out of the best plane through the residual SbC 3 fragment. As result, in addition to the chirality at antimony, this folding induces planar chirality (with the aromatic ring and the nitrogen atom as chiral plane and pilot atom, respectively; for planar chirality the enantiomers are given as pS N and pR N ).…”

“…8 However, the uorination was effective when the dibenzoazastibocine chloride MeN(CH 2 C 6 H 4 ) 2 SbCl was reacted with KF in DMF solution. 9 While the partial phenylation of SbF 3 with PhLi or PhMgBr reagents failed, the isolated product always being Ph 3 Sb regardless of the molar ratio of the reagents used, 8 for other organolithium reagents the reaction with SbF 3 led to the desired organoantimony(III) uorides, [10][11][12] even if the stoichiometry could not be fully controlled and from the reaction mixture both R 2 SbF and RSbF 2 were isolated by fractional crystallization, e.g. for R ¼ 2,4,6-t Bu 3 C 6 H 2 .…”

Reversible Oxidative Se−Se Coupling of Phosphine Selenides by Ph3Sb(OTf)2

“…Interestingly,N MR studies of the reactions of 2 with Ph 3 Sb (Scheme 1d)i ndicate that this redox process is reversible, demonstrating the versatilityo ft his redox behaviour of antimony.S imilar redox behaviour has only been reported for antimony in conjunctionw ithagold center,f or which Gabbai et al reportedareversible umpolung of the SbÀAu bond upon reduction/oxidation. [8] Mixtures of two equivalentso fiPr 3 PSe with Ph 3 Sb(OTf) 2 in dichloromethane at RT show ab road signal in the 31 P{ 1 H} NMR spectrum (70.4 ppm, 1 J PSe = 663 Hz). The difference in chemical shift relative to the sharp signal for iPr 3 PSe (68.9 ppm) [9] is small,b ut when cooled to 187 K, three separates ignals are observed ( Figure 1).…”