Sterically Crowded, Rigid,C₃Symmetric Phosphites:  Synthesis, Structure, and Preparation of Metal Complexes

Abstract

The sterically congested, rigid, C 3 symmetric phosphites (2a-e) have been synthesized by reaction of PCl 3 with the corresponding tris(3,5-dialkyl-2-hydroxyphenyl)methanes (3,5-di-tert-butyl; 3-tert-butyl-5-methyl; 3,5-di-tertpentyl; 3-adamantyl-5-methyl; 3,5-dimethyl) and characterized. The arsenite derivative (3b) of tris(3-tert-butyl-5-methyl-2-hydroxyphenyl)methane was similarly prepared by reaction with AsI 3 . Both the phosphite 2a and the arsenite derivative 3b have been examined by single-crystal X-ray analyses. Metal complexes (4-6) of the phosphites were prepared by reaction of the phosphite with [PdCl 2 (cod]) (cod ) 1,5-cyclooctadiene), [PdCl(η 3 -C 3 H 5 )] 2 and [Rh(CO) 2 (acac)] (acac ) acetylacetonate), respectively, and examples of each are represented by X-ray structure determinations.

Cage‐Shaped Borate Esters with Tris(2‐oxyphenyl)methane or ‐silane System Frameworks Bearing Multiple Tuning Factors: Geometric and Substituent Effects on Their Lewis Acid Properties

“…For 1 a B⋅THF, the significant upfield shift of the methine hydrogen was confirmed relative to that of 1 a H 3 (6.07→5.13 ppm). This shift has been observed for similar cage‐shaped compounds 17. The chemical shift δ ( 13 C) of the methine carbon of 1 a B⋅THF was observed at 57.4 ppm (38.4 ppm for 1 a H 3 ) 17.…”

“…This shift has been observed for similar cage-shaped compounds. [17] The chemical shift dA C H T U N G T R E N N U N G ( 13 C) of the methine carbon of 1 aB·THF was observed at 57.4 ppm (38.4 ppm for 1 aH 3 ). [17] The ligated THF showed broadening and downfield-shifted signals at d( 1 H) = 4.46 and 2.13 ppm (free THF: d( 1 H) = 3.73 and 1.84 ppm).…”

“…[17] The chemical shift dA C H T U N G T R E N N U N G ( 13 C) of the methine carbon of 1 aB·THF was observed at 57.4 ppm (38.4 ppm for 1 aH 3 ). [17] The ligated THF showed broadening and downfield-shifted signals at d( 1 H) = 4.46 and 2.13 ppm (free THF: d( 1 H) = 3.73 and 1.84 ppm). The boron NMR signals appeared at dA C H T U N G T R E N N U N G ( 11 B) = 5.52 ppm for 1 aB·THF, while the open-shaped borate BA C H T U N G T R E N N U N G (OPh) 3 appeared at 16.52 ppm.…”

1,2,4-Triazine-picolinamide functionalized, nonadentate chelates for the segregation of lanthanides(iii) and actinides(iii) in biphasic systems

“…1). [39][40][41][42][43] Additionally, the triphenoxymethane scaffold allows facile synthetic modulation of the alkyl substitution on the platform by choice of 2,4-substituted phenol.…”

P‐Chiral Monodentate Diamidophosphites − New and Efficient Ligands for Palladium‐Catalysed Asymmetric Allylic Substitution

“…[34] and references cited therein). The IR (Table 3), [35] 13 C NMR (for the allyl ligand), [36] and MS spectroscopic data (see Exp. Sect.)…”