Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes

Abstract

Fluoroarene complexes of the small bite angle bisphosphine Cy 2 PCH 2 PCy 2 (dcpm) have been prepared: [Rh(dcpm)(η 6

Reversible Encapsulation of Xenon and CH2Cl2 in a Solid‐State Molecular Organometallic Framework (Guest@SMOM)

“…Addition of NBD to [Rh(Cy 2 PCH 2 PCy 2 )(1,2‐F 2 C 6 H 4 )][BAr F 4 ] and crystallisation from a CH 2 Cl 2 /pentane mixture yielded orange prismatic crystals (86 % yield). Single‐crystal X‐ray diffraction, elemental analysis, solution and solid‐state NMR (SSNMR) spectroscopic data confirmed the formulation as a diene complex [Rh(Cy 2 PCH 2 PCy 2 )(η 2 η 2 ‐NBD)][(CH 2 Cl 2 ) 0.75 ⊂BAr F 4 ] ( [2‐NBD][(CH 2 Cl 2 ) 0.75 ⊂ BAr F 4 ] ) .…”

Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]+ Cations, and their use in Synthesis and Catalysis

“…1 HNMR spectra collected in deuterated solvents were referenced to residual protio solvent. 1 HNMR spectra collected in neat PFB were referenced to literature values [13] or the center of the solvent resonance (1,2,3,4-F 4 C 6 H 2 , d = 6.93;F 5 C 6 H, d = 6.92). 31 Pand 19 FNMR spectra were referenced against 85 %H 3 PO 4 (external) and CCl 3 F( external), respectively.C hemical shifts (d)a re quoted in ppm and coupling constants (J)i nH z. ESI-MS were recorded on aB ruker MicrOTOFi nstrument interfaced with ag lovebox.…”

“…Havinge stablished an effective route to h-bound PFB complexeso f{ Rh(Cy 2 PCH 2 CH 2 PCy 2 )} + we soughtt od emonstrate their synthetic utilityf or the preparation of new complexes with other weakly-boundl igands. We À10.9 167 À146.7, À167.1 [13] 2a [a] À10.4 168 À146.3 [13] 1a [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(h 2 h 2 -NBA)][BAr F 4 ]( NBA = norbornane), with isobutene. [15] The isobutenei nteracts with the metal center through an alkene and an agostic interaction.…”

“…acetone) there are instances when substitution does not take place as the arene binds too strongly, especially with smaller bite‐angle diphosphine ligands. To overcome this we have recently reported the first structurally characterized metal complex with a weakly binding 1,2,3‐F 3 C 6 H 3 ligand, [Rh(Cy 2 PCH 2 PCy 2 )(1,2,3‐F 3 C 6 H 3 )][Al{OC(CF 3 ) 3 } 4 ] 3 a (Scheme ) . Displacement of the fluoroarene by H 3 B ⋅ NMe 3 generates the corresponding sigma amine‐borane complex.…”

“…acetone) there are instances when substitution does not take place as the arene binds too strongly, [11e] especially with smaller biteangle diphosphinel igands. To overcomet his we have recently reportedt he first structurally characterizedm etal complex with aw eakly binding 1,2,3-F 3 C 6 H 3 ligand, [Rh(Cy 2 PCH 2 PCy 2 )(1,2,3- [13] Displacement of the fluoroarene by H 3 B·NMe 3 generates the corresponding sigma amine-borane complex. The use of the non-coordinating [Al{OC(CF 3 ) 3 } 4 ] À anion, popularized by Krossing, [14] is crucial to this reactivity, as the more commonly-used [BAr F 4 ] À anion binds competitively with both 1,2,3-F 3 C 6 H 3 and the amineborane H 3 B·NMe 3 ,thus quenching reactivity.…”