4, 4′‐ and 5, 5′‐Functionalized (S)‐ and (R)‐2, 2′‐Bis(diphenylphosphanyl)‐1, 1′‐binaphthyl Oxide Derivatives

Abstract

A series of 4, 4′‐ and 5, 5′‐functionalized (S)‐ and (R)‐2, 2′‐bis(diphenylphosphanyl)‐1, 1′‐binaphthyl oxide (BINAPO) derivatives were prepared by Suzuki‐Miyaura coupling from 4, 4′‐ and 5, 5′‐dibromo‐BINAPO and the corresponding boronic acid, RB(OH)2 [R = 4‐(methoxycarbonyl)phenyl, 3‐pyridyl and 4‐pyridyl]. The carboxylic acid‐substituted BINAPO derivatives were obtained from the esters by saponification with NaOH. The novel BINAPO derivatives were fully characterized by NMR (1H, 13C, 31P), IR spectroscopy, and mass spectrometry, and for (S)‐4, 4′‐bis(3‐pyridyl)‐BINAPO, (S)‐5, 5′‐bis(3‐pyridyl)‐BINAPO, and (S)‐ and (R)‐4, 4′‐bis(4‐carboxyphenyl)‐BINAPO also by X‐ray crystallography. They are thermally stable up to 400–440 °C as determined by DTA/TG analysis.

Synthesis, structure and luminescence properties of a cadmium(ii)-based coordination polymer with (S)-4,4′-bis(4-carboxyphenyl)-2,2′-bis(diphenylphosphinoyl)-1,1′-binaphthyl as chiral linker

“…The dihedral angles between the binaphthyl rings are slightly smaller (76.7(3) and 79.6(4)°) than the dihedral angle of the free ligand (82.05(4)°). 22 Furthermore, one water molecule is coordinated to Cd2 (Cd2-O13 2.409(8) Å) ( Fig. 1a).…”

“…No mass loss was detected between 200 and 400°C, confirming the thermal stability of 1 up to 400°C. Gradual decomposition occurred above 400°C; the free ligand H 2 L is thermally stable up to 420°C 22 (see ESI †).…”

Noble Metal Complexes with 4, 4′‐ and 5, 5′‐Pyridyl‐Functionalized (S)‐2, 2′‐Bis(diphenylphosphanyl)‐1, 1′‐binaphthyl Ligands

“…The ligands ( S )‐4, 4′‐ ( L 1 ) and ( S )‐5, 5′‐bis(3‐pyridyl)‐2, 2′‐bis(diphenylphosphanyl)‐1, 1′‐binaphthyl ( L 2 ) were prepared by reduction of ( S )‐4, 4′‐ and 5, 5′‐bis(3‐pyridyl)‐2, 2′‐bis(diphenylphosphinoyl)‐1, 1‐binaphthyl,21 according to a modified literature procedure 22. The 31 P{ 1 H} NMR spectra showed a high‐field shift from about 28 ppm (BINAP‐oxides) to –15.1 ppm ( L 1 , L 2 ).…”

“…CDCl 3 was dried with LiAlH 4 , distilled and kept over molecular sieves. [Pd(PPh 3 ) 4 ],28 [AuCl(tht)],29 [PdCl 2 (cod)],30 [PtI 2 (cod)],30,31 ( S )‐4, 4′‐ and 5, 5′‐bis(3‐pyridyl)‐2, 2′‐bis(diphenylphosphinoyl)‐1, 1‐binaphthyl21 were synthesized according to literature procedures. [Ti(O i Pr 4 )], tetramethyldisiloxane (TMDS) and trichlorosilane (HSiCl 3 ) were used as purchased under inert conditions.…”

“…Preparation of L 1 and L 2 : The corresponding phosphine oxide21 of L 1 or L 2 (2.04 g, 2.52 mmol, 1 equiv.) and Na 2 SO 4 as drying agent (10 wt.‐ %, 0.204 g) were suspended in dry toluene (50 mL) and TMDS (2.23 mL, 12.6 mmol, 5 equiv.)…”