No abstract

The title compounds of the type P(RNCH2CH2)3N (1, R = H; 2, R = Me; 3, R = CHz2Ph) display the unexpected basicity trend 1 < 2 < 3 with respect to protonation which forms the azaphosphatranes (4, R = H; 5, R = Me; 6, R = CH2Ph). The unusual basicity order 1 < 2 < 3 is also supported by the trend in 1JPSe values obtained for SeP(RNCH2CH2)3N (8, R = H; 9, R = CH2Ph; 10, R = Me). Deprotonation of 4 is shown to produce a variety of deprotonated derivatives which were trapped by alkylation with MeI. A favored rationale for the unusual weakness of 4 as a protonic acid (pKa in DMSO, 29.6) is an unusual stability of the axial three‐center four‐electron bond signalled by the unusually high field 31P chemical shift of this cation (—42 ppm).

We have recently described the extraordinary Lewis basicity of the phosphorus in 1 for protons to produce the unexpectedly weak conjugate acid 2.1-7 The transannulation process that

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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.