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Metal Coordination to the Formal PN Bond of an Iminophosphorane and Charge‐Density Evidence against Hypervalent Phosphorus( V )
Author(s) -
Kocher Nikolaus,
Leusser Dirk,
Murso Alexander,
Stalke Dietmar
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400163
Subject(s) - hypervalent molecule , chemistry , metal , phosphorus , formal charge , reagent , stereochemistry , covalent bond , organic chemistry
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.