Journal
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
Volume 638, Issue 7-8, Pages 1103-1108Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/zaac.201200123
Keywords
P4 activation; Phosphorus; Cations; Main group elements; Structure elucidation
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Funding
- Fonds der Chemischen Industrie (FCI)
- European Phosphorus Science Network (PhoSciNet) [CM0802]
- Deutsche Forschungsgemeinschaft (DFG) [WE 4621/2-1]
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The reaction of several amino-substituted mono- and dichlorophosphanes (R2N)nPCl3n (n = 2, R = i-Pr; n = 1, R = i-Pr, Cy) with GaCl3 to form phosphenium cations [(i-Pr2N)2P]+ (13+) and [(R2N)PCl]+ (14a, b+) has been investigated. The isolation and fully characterization of the first amino- and chloro-substituted phosphenium cation 14b[GaCl4] was accomplished. The insertion of these phosphenium ions into PP bonds of dissolved P4 was examined. Amino- and chloro-substituted phosphenium cations 14a, b+ readily form the corresponding P5+-cages 15a, b+. No reaction was observed for the less electrophilic diamino-substituted phosphenium cation 13+. The molecular structures of [14b][GaCl4] and [15b][Ga2Cl7] are presented and, furthermore, the intriguing NMR spectra of the P5+-cations 15a, b+ are discussed.
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