Metal Coordination to the Formal PN Bond of an Iminophosphorane and Charge-Density Evidence against Hypervalent Phosphorus(V)
✍ Scribed by Nikolaus Kocher; Dirk Leusser; Alexander Murso; Dietmar Stalke
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 311 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
Abstract
The iminophosphorane Ph~2~P(CH~2~Py)(NSiMe~3~) (1) was treated with deprotonating alkali metal reagents to give [(Et~2~O)Li{Ph~2~P(CHPy)(NSiMe~3~)}] (2), [{Ph~2~P(CH~2~Py)(NSiMe~3~)}Li{Ph~2~P(CHPy)(NSiMe~3~)}] (3) and [{Ph~2~P(CH~2~Py)(NSiMe~3~)}Na{Ph~2~P(CHPy)(NSiMe~3~)}] (4). We report their coordination behaviour in solid‐state structures and NMR spectroscopic features in solution. Furthermore, we furnish experimental evidence against hypervalency of the phosphorus atom in iminophosphoranes from experimental charge‐density studies and subsequent topological analysis. The topological properties, correlated to the results from NMR spectroscopic investigations, illustrate that the formal PN double bond is better written as a polar P^+^N^−^ single bond. Additionally, the effects of metal coordination on the bonding parameters of the iminophosphorane and the related anion are discussed.