Pyridine, thiophosphine, and selenophosphine complexes of the phenylphosphine dication

Abstract

Compounds of the generic formula [PhPL][OTf]2 with L = bipyridine (bipy) and 4,4′-di(tert-butyl)-2,2′-bipyridine (Bbipy) and [PhPL2][OTf]2 with L = 4-dimethylaminopyridine (dmap), tricyclohexyl-thiophosphine, and tricyclohexyl-selenophosphine have been prepared by the reaction of dichlorophenylphosphine with two equivalents of trimethylsilyl triflate and the respective ligand. The new complexes of the phenylphosphine dication with this variety of ligands expands the scope of coordination complexes involving phosphorus as an acceptor.

Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable PIII Lewis Acid

“…Compounds 1[X] 2 (X = OTf and B(C 6 F 5 ) 4 )w ere prepared according to Scheme 1a. [14] The 31 PNMR spectra of the cations showeds inglets at d P = 131 and 144 ppm, respectively,f or the triflate and borate salts, and these values are consistent with values for other tricoordinateP III polycations. [7] The structure of 1[OTf] 2 was determined in the solid state by single-crystal diffraction confirming the pyramidal environment around the phosphorus atom ( Figure 1a).…”

“…Compounds 1 [X] 2 (X=OTf and B(C 6 F 5 ) 4 ) were prepared according to Scheme a . The 31 P NMR spectra of the cations showed singlets at δ P =131 and 144 ppm, respectively, for the triflate and borate salts, and these values are consistent with values for other tricoordinate P III polycations .…”

Tris(benzoimidazol)amine (L) complexes of pnictogen(iii) and pnictogen(v) cations and assessment of the [LP]3+/[LPF2]3+ redox couple

“… 2 A variety of pnictogen( iii ) based cations have been synthesized by halide abstraction from PnX 3 derivatives in the presence of various ligands and weakly coordinating anions. 3 The cationic charge of such complexes not only lowers the energy of the pnictogen based LUMO but also lowers the energy of the HOMO, so that oxidation is impeded. Consequently, examples of redox couples of the type [Pn( iii )L] 3+ /[Pn( v )R 2 L] 3+ have not yet been reported.…”

Direct Synthesis of Dibenzophospholes from Biaryls by Double C–P Bond Formation via Phosphenium Dication Equivalents

“…Actually, the almost same signal (δ 180 ppm) appeared by simple mixing of PhPCl 2 (δ 161 ppm) and 2.0 equiv of AgOTf (Figure S16), thus suggesting that the former is PhP­(OTf) 2 . However, the reported 31 P­{ 1 H} chemical shift of the latter PhP­(DMAP) 2 (OTf) 2 in CD 2 Cl 2 is δ 121 ppm, which is not fully consistent with the observed value. Given the labile and reversible coordinating nature of monodentate DMAP under Tf 2 O-mediated conditions, we then tested the more rigidly coordinating tridentate terpyridine derivative t -Bu-terpy instead of DMAP (Scheme ).…”