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N ‐Thiophosphorylated and N ‐Phosphorylated Iminophosphoranes [R 3 P=N–P(X)R′ 2 ; × = O, S] as Models for Dendrimers: Synthesis, Reactivity and Crystal Structures
Author(s) -
Larré Christophe,
Donnadieu Bruno,
Caminade AnneMarie,
Majoral JeanPierre
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199904)1999:4<601::aid-ejic601>3.0.co;2-x
Subject(s) - chemistry , dendrimer , reactivity (psychology) , phosphorylation , crystal structure , crystal (programming language) , stereochemistry , combinatorial chemistry , polymer chemistry , crystallography , biochemistry , medicine , alternative medicine , pathology , computer science , programming language
Several R 3 P=N–P(X)R′ 2 and Fe[C 5 H 4 Ph 2 P=N–P(X)R′ 2 ] 2 derivatives (X = S, O) are readily obtained from Staudinger reactions between phosphanes and N 3 –P(X)R′ 2 . The P=N–P=X groups are easily alkylated on the × atom with methyl or isopropyl triflates. The alkylation induces a lengthening of the P–X bond, as shown by X‐ray diffraction studies. This corresponds to a weakening of the P–X bond which can be cleaved with P(NMe 2 ) 3 to yield [P=N–P : ] linkages. The presence of tricoordinated phosphorus atoms opens the way to a versatile reactivity, including the reaction with alkyl iodides and functionalized azides. These molecules are good models for screening which types of reagents and reactions could be used with macromolecules possessing also P=N–P=X linkages, such as dendrimers.