Determination of the Stereoelectronic Parameters of PF₃, PCl₃, PH₃, and P(CH₂CH₂CN)₃. The Quantitative Analysis of Ligand Effects (QALE)

Abstract

Using the QALE model, we determined the electronic parameters for PF3 (χd = 44 ± 4, E ar = 0, πp = 14 ± 1), PCl3 (χd = 42 ± 1, E ar = 4.1 ± 0.3, πp = 5.3 ± 0.5), PH3 (χd = 17 ± 1, E ar = 0, πp = 3.7 ± 0.7), and P(CH2CH2CN)3 (χd = 17.0 ± 0.6, E ar = 0, πp = 1.2 ± 0.2). These values indicate that PF3 and PCl3 are comparable in σ donor ability and are the poorest σ donor ligands we have studied. Both PH3 and P(CH2CH2CN)3 are reasonably good σ donors, comparable in strength to P(p-ClC6H4)3. PF3 is by far the best π acid. The π acidity of PCl3 is comparable to that of P[(OCH2)3]CEt, whereas the π acidity of PH3 is intermediate between P(O-p-XC6H4)3 and P(OR)3. The analysis of data sets containing PZ3 - i H i sometimes requires the inclusion of “i” as a parameter, which we connect with changes in hybridization of these ligands. There are good correlations of χd and πp with the theoretical results of Gonzalez-Blanco and Branchadell and those of Fantucci. The stereoelectronic parameters for 107 PZ3 species are listed.

Understanding the electron-stimulated surface reactions of organometallic complexes to enable design of precursors for electron beam-induced deposition

“…16) [64], but with a new P-R bond that has the potential to improve precursor stability and thus suitability for EBID. This approach is supported by the successful synthesis of ClAuPF 2 R complexes [65], although no EBID studies with these organometallic precursors have been reported.…”

Stereoselective cyclization of silylated epoxy aldehydes into piperidines. Effect of the silicon group

“…For example, after protection of the secondary alcohol of 11a as a silyl ether, the ester group of 14 could be smoothly reduced using LiAlH 4 . After 1h at 0°C in Et 2 O, the primary alcohol 15 could be isolated in 84% yield (Scheme 11).…”

“…The solution was stirred 3 days at room temperature. Then aqueous NH 4 Cl was added and the aqueous layer was extracted with Et 2 O. The organic layer was washed with brine, dried over MgSO 4 and concentrated.…”

Backbone Diversity Analysis in Catalyst Design

“…Choosing relevant descriptors is a challenge. [16,[36][37][38] Descriptors can be determined either from the molecular structure, or the physical properties. [14] Table 1 shows some typical examples of molecular descriptors for the complex shown in Figure 4.…”