A convenient one‐pot synthesis of 1,2‐azaphospholanium salts

(Isopropylamino)(methyl)diphenylphosphonium iodide

“…Amidophosphonium salts are useful precursors for phosphazenes, which are necessary for the aza-Wittig reaction. They can be synthesized by different methods: addition of alkylhalides or methyltriflate to a phosphorus-nitrogen-single bond (Payne et al, 1965;Mizuta et al, 2007), addition of alkylhalides to a phosphorus-nitrogen double bond (Imrie et al, 1995), via intramolecular addition of alkylhalides (Aladzheva et al, 2003) or via other routes (Demange et al, 2006). We became interested in this class of compounds, because the starting compound Ph 2 PN( i Pr)P(Ph)N( i Pr)H acts as a superb ligand in the chromium catalyzed trimerization of ethene (Peitz et al, 2010).…”

“…For the synthesis of Ph 2 PN( i Pr)P(Ph)N( i Pr)H, see: Peitz et al (2010). For the structures of amidophosphonium salts with similar substituents, see: Payne et al (1965); Imrie et al (1995); Aladzheva et al (2003); Demange et al (2006); Mizuta et al (2007). Table 1 Hydrogen-bond geometry (Å , ).…”

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

“…Aladzheva and colleagues reported an easy access to the 1,2-azaphophanolanes species 153 – 156 , by the one-pot reaction between the corresponding 3-halopropylamine hydrohalides and 2 equiv of PPh 2 Cl in the presence of an excess of NEt 3 to scavenge the HCl formed (Scheme ). Although these ligands do not possess an additional P-donor function, they belong to N -functionalized DPPA-type ligands, involving a P atom (PR 4 + moiety). The iodide 155 and the perchlorate 156 derivatives could be isolated in good yield (>80%), and the authors provided their complete FT-IR and 1 H and 31 P NMR spectroscopic characterization.…”

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation–acetalization of olefins

“…It is noted that the gauche conformation of the C26-C27 bond is observed in Rh-L2, and the O-atom is projecting inward towards the PIJV) + -atom (P2). The P2-O4 distance (3.45 Å) is significantly shorter than the sum of the Allinger radii of P and O (P, 2.22 Å; O, 1.82 Å), 34 indicating the chemical bonding interaction in the P⋯O linkage due to the available Lewis acid-base pair interaction between the PIJV) + -site and the O-atom in the ether moiety.…”

“…The co-planar structure for the PIJV) + -N-PIJIII) skeleton in which the bond distance of N1-P2 [P2 = PIJV) + ] [1.671(3) Å] is much shorter than that of N1-P1 [P1 = PIJIII), 1.746(3) Å)] has been observed before. 34 The structural information of Rh-L2 indicates that the bifunctionalities of the phosphine fragment and the Lewis acidic phosphonium in L2 are well retained without incompatibility problems. However, the acidity of phosphoniums in L2 is able to be quenched by the accessible electron-rich ether group when they are located in sterically convenient positions.…”