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Reaction of Tungsten–Phosphinidene and –Arsinidene Complexes with Carbodiimides and Alkyl Azides: A Straightforward Way to Four‐Membered Heterocycles
Author(s) -
Seidl Michael,
Kuntz Christian,
Bodensteiner Michael,
Timoshkin Alexey Y.,
Scheer Manfred
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201410191
Subject(s) - phosphinidene , chemistry , alkyl , medicinal chemistry , tungsten , nuclear magnetic resonance spectroscopy , stereochemistry , mass spectrometry , single crystal , crystallography , organic chemistry , chromatography
The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO) 5 } 2 ] (E=P ( 1 a ), As ( 1 b ); Cp*=C 5 Me 5 ) with carbodiimides leads to the new four‐membered heterocycles of the type [Cp*C(NR) 2 E{W(CO) 5 } 2 ] (E=P: R=iPr ( 2 a ), Cy ( 3 a ); E=As: R=iPr ( 2 b ), Cy ( 3 b )). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete derivatives [Cp*P{W(CO) 5 }N(R)NN{W(CO) 5 }] (R=Hex, Cy) ( 4 ). These unprecedented N 3 P four‐membered triazaphosphete complexes can be regarded as stabilized intermediates of the Staudinger reaction, which have not been previously isolated. All of the isolated products were characterized by NMR, IR spectroscopy, mass spectrometry, and by single‐crystal X‐ray diffraction analysis.