Aroylphosphanes: Base‐Free Synthesis and Their Coordination Chemistry with Platinum‐Group Metals

Abstract

Aroylphosphanes: base-free synthesis and their coordination chemistry with platinum-group metals

The story of acyl phosphines: Synthesis, reactivity, and catalytic applications

“…Saunders to the previous observation, a small increase in ν(CO) is observed upon coordination to metal centers in all cases. [30] Kumar et al presented the reaction between bidentate bis (acyl phosphine) ligands 20a and 20b with [Pd(η 3 -C 3 H 5 )Cl] 2 which leads to the formation of binuclear Pd (II) complex [Pd 2 (η 3 -C 3 H 5 ) 2 Cl 2 {1,3-{Ph 2 PC (O)} 2 (C 6 H 4 )}] (119) as depicted in Scheme 33. On the other hand, the reaction of ligand 20a with [Pd(COD)Cl 2 ] in the presence of AgClO 4 resulted in the formation of a PCP-type pincer complex, [PdCl{2,6-{Ph 2 PC(O)} 2 (C 6 H 3 )}] (120) via C-H bond activation in good yield.…”

“…Further, the synthesis of acyl phosphines 20a, 20c, and 21 via condensation of acid chlorides and diphenylphosphine even in the absence of base was achieved successfully as shown in Scheme 4. [30] 7λ 3 -phosphanorbornadienes are considered as a potential source of metastable singlet phosphinidenes, which can further be utilized for the preparation of various phosphorus compounds. [31] It was initially observed that the 7λ 3 -phosphanobornadiene can be used only when lone pair of phosphorus is protected.…”

“…The 31 P{ 1 H} NMR spectra of these complexes showed doublets around δ 36 ppm with a 1 J Rh-P coupling of $146 Hz. [30] S C H E M E 3 0 i. [Cp*IrCl 2 ] 2 , THF, Δ, 1 h; ii.…”

Ylide-Substituted Phosphines with a Cyclic Ylide-Backbone: Angle Dependence of the Donor Strength

“…Several advances in homogeneous catalysis over previous decades have been driven by this fact. 4 , 5 For systematic ligand design various metrics are used in order to describe the electronic and steric properties of phosphine ligands, including the Tolman electronic parameter (TEP), 6 , 7 cone angle, and the buried volume. 8 These measures facilitate the understanding of structure activity relationships in catalysis and build the foundation to computer-aided catalyst design.…”

η1:η2-P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)

“…First described in 1985 [24], such systems remain relatively rare, though-with the exception of type E-all possible motifs have been realized, with P-metalla-(type A) and C-metalla-(type B) systems the most heavily studied. Recently, as part of an extended program investigating transition metal compounds featuring low-coordinate phosphacarbons with potential for conjugation [25][26][27][28], we have prepared and studied a range of ruthenaphosphaalkenyl complexes of the type [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] (R = Me 1a, Ph 1b, Tol 1c) [29,30]. These are prepared by hydroruthenation of phosphaalkynes R3SiC≡P, following from methodology developed initially by Hill and Jones for t BuC≡P and related systems [31][32][33], and superficially related to Nixon's independent reduction of [(Ph3P)2Pt(η 2 -P≡C t Bu)] with Schwartz's reagent [34].…”